I have tried this in two ways in the past. I think of the two, only one will be of use for your objective.
PC Villain in the Group
Create the villain with its player and discuss what their villainous goal actually is. Ensure the player can and will commit to being a villain. Their goal should require the villain to need to be close to or involved with the players to achieve. You will probably want the nature of your villain to be a big revelation at some stage of the campaign, so they need strong hooks to tie them to the heroes, and to tie them to what the heroes are trying to do.
Of course, the heroes will want to achieve a positive outcome in the scenario, while their supposed "friend and fellow hero" is actually trying to ensure a negative outcome. This ensures challenge for each player without necessitating that the players be targetting each other, limiting the sense of mutual dependence, or requiring that the relationship be entirely based on lies.
In truth, the variance between the heroes and the villain might only a slight difference in ideology, the burden of a dark family secret, or the interplay of noble but misguided intentions.
Example:
*Over time the group learns that an ancient prophecy claims a soul-collecting terror from ages past will rise again to plague a small village on the ancestral lands of one of the characters.
As they uncover more and more about the prophecy, they realize that the time will soon arrive. They must act now. They become desperate to discover a way to prevent or guard against the soul-collector.
Throughout this period, the villain is aware that it was their many times great grandmother which unleashed this foul curse on the village in the first place to spare her own children from the ravages of the soul-collector. If the villain chooses to delve deeper into the lore of the family, they will discover much more about the monster than the heroes, including that it was bound by the family to both stop greater depredations and to extract special favors from it. They can, if they have the will, learn how to bind it, and become tempted by what the being will offer for even a little bit of freedom. They will also learn that if the monster is balked it will come for them, their siblings, and other members of that generation within the family and nothing will be able to stop it. Worse, if they reveal the family secret they will be disowned, the monster will take back all the gifts it provided the family, and it will be set loose to kill indiscriminately. To ice the cake, if the villain chooses to master the rites involved, they can gain direct control of the monster and earn their own, very special favors from it.
The heroes will of course be committed to stopping the creature, and their flawed understanding of the situation will enable the villain, if they stick close to the heroes, to monitor progress and to try to redirect it when necessary to prevent success.*
Requirements
This style of scenario best pits character goal versus character goal, but not character versus character explicitly. It does not need to require that the villain receive lots of useful extra knowledge, nor that they go off for extended periods to plot or take care of things off-screen. Moreover, it allows all the players to play toward a goal of uncertain resolution, rather than forcing one of them to be a glorified NPC just there to trick the players. A great scenario will have lots of conflicting emotions on both sides of the group as the course of events plays out.
Key Points
- Everyone plays in the scenario, no ringers or PCNPCs
- Each has a related goal that they may or may not achieve
- once play starts there is no meta-fiddling with the villain's
knowledge or activities
- the heroes may remain focused on ending the threat little knowing
they have a viper in their midst
- the villain has the burden of keeping their secret agenda of foiling
the goal of the heroes without getting caught
At the end, there is a chance for a dramatic conclusion when the duplicity of the villain ultimately comes to light. If the bonds between all the PCs are tight, the heroes may even be swayed to the villain's side...
The two questions you should ask are:
whether it's the player or the character that's uncomfortable with your proposed shift in mood, and
if it's the latter, whether your players would be OK with the kind of intra-party conflict the shift would generate.
Is the player really OK with it?
If your player is uncomfortable with the campaign turning evil (or at least morally ambiguous) and just "doesn't want to go there", then I'd generally suggest not going there. You started the game with characters that are noble heroes, and all your players seem at least OK with that — you shouldn't change that in the middle of the campaign, unless you're sure your players will be OK with the new theme, too.
If you do still want to try the mood shift, please do make sure to talk things out clearly with the objecting player. Even if they say that it's their character who wouldn't go along with an evil plot, they could be using that as a cover for personal unwillingness to explore such themes. Just make it clear — preferably in private — that they can say "no" if they want, and that you'll respect it.
(Also, no discussion of game themes and intra-group tensions would be complete without a link to the Same Page Tool, so here it is.)
So the player is OK with it, but their character isn't. Now what?
So you have five nominally good characters who are increasingly tempted to "cut corners" and use questionable means to achieve their ends, and one who refuses to do anything of the sort. That's a great recipe for lots of tension between the party members.
This can be a good thing or a bad thing. It can be bad because it requires a tricky balancing act between party cohesion and inter-character conflict, and maintaining that balance can require some skill from both the GM and the players.
On the other hand, it can be good because, done well, it can be really fun to play and makes for great plots.
Note that such conflict doesn't necessarily have to turn into an actual PvP fight (which, based on what I've heard, would generally be a bad idea in 4e anyway). In fact, I'd suggest that, at least 99% of the time, this is something you shouldn't let happen, just like you generally wouldn't let the party get all killed by falling rocks or let the characters just split up and go their separate ways. It just doesn't make for a fun game.
Instead, if you want to try this, you and your players should agree in advance, out of game, to never let things get quite so far that a fight (or a party split) would be unavoidable. This means that the other players — and their characters — need to stay aware of the fact that they need the "pure" character's help (for some reason; preferably a plausible one) and that they therefore have to stop just short of doing anything that this character would find totally unacceptable.
It also means that the player playing that character has to be OK with the fact that their character also, for some reason, needs to cooperate with the others, even if he (the character, that is!) is feeling distinctly uncomfortable about it.
This does require a certain amount of "meta-game" communication between players, and possibly some creative adjustment of character behavior or even plot events to avoid escalating the tension too far. Do tell your players that it's perfectly OK to, say, ask another player out-of-game how their character would react to a particular action by another character, or even to just raise a hand and say "Guys, please don't do that, there's no way my character wouldn't righteously smite you if you did it."
Best Answer
In my experience and from reviewing many sites and DM pages, this is not a good idea. It would be a great player to not metagame in this scenario. The campaign could break if they aren't able to separate player knowledge and character knowledge.
What you could do is run a separate campaign for another separate group of players in an "evil campaign". Then later at the end of the campaign bring both groups together for the final showdown. You would want to limit the amount of players in both groups so it wouldn't bog down the game in the end. You could even have an evil PC come in at different times to frustrate the other group or vice versa.
I would recommend that you let the players in both groups know what is going on so when one group loses at the end they won't be too upset.