Well, yes you can get 'stuck', but it depends on the version.
For instance, in the first Gen II versions Gold/Silver/Crystal, you can get stuck.
Here's a gif from Pokemon Gold I made some moment ago. (the gif is quite big)
The main way I see it is when you are 'stuck' on an island where you require at least Surf to get off it and you don't have any Pokemon to use Surf or can teach it to since you released all the Pokemon who could.
In Red/Blue/Yellow, you have Cinnabar Island and in Gold/Silver/Crystal, you have Cianwood City.
As for Generation III games and remakes of previous games, there's a feature which prevents you from releasing some of the Pokemon, especially those which have Surf, Dive of Fly.
Here's another gif of Pokemon Emerald I made some moment ago. (that one's quite big as well)
The Pokemon will even keep the move in some cases (the Lanturn in the second gif refused to forget Surf at the move deleter). That means that as from Ruby/Sapphire/Emerald, there's a way you can go back and train your Pokemon until it levels up and be able to fight the trainer, though that might be extremely tedious (you'll perhaps have to save at every step when walking through tall grass/surfing) and go to a place where the wild Pokemon is of a reasonable level to train your current Pokemon.
Quoted from bulbapedia, emphasis mine:
A set amount of strolling NPCs, known as the player's fans (Japanese: ファン fan), will arrive at the avenue each day. This amount is determined by the avenue's rank and the player's game progression. After the player has entered the Hall of Fame, Gym Leaders will occasionally arrive among these, as a bonus.
Immediately later in the same paragraph:
The avenue can hold no more than twelve visiting NPC fans at a time. Consequently, no NPC fans will arrive on a day on which this limit has already been reached, even if the player subsequently makes room. This also means that any amount of arriving NPC fans that would have otherwise exceeded the limit will be capped.
The above explains why you have as much as 12 fans.
I don't know the exact formula that determines how the number of fans should be each day, but it seems to be related to your avenue rank, the number of badges you have, and main story checkpoints.
The NPC fans between themselves otherwise seem to be unlocked randomly, meaning that you probably don't need to reach a certain point for unlocking this or that NPC (besides those unlocked by entering the Hall of Fame for the first time).
I also found this on pokemongts:
To get fans to come to Join Avenue, the player needs to become "popular" by the game's standards. This means becoming famous via Pokestar Studios, doing Pokemon Musicals, and doing well in the Pokemon World Tournament and Battle Subway.
Unfortunately, I cannot exactly confirm this, but at least, now you know when you can stop waiting so you don't "sit here waiting" when you've progressed in-game.
If you want to get fans that are not in-game generated, you still have a maximum of 12 fans per day (This also means that you if you have 12 fans who visit due to player interactions, you won't be receiving in-game fans on that day).
For instance, there is this method named Magnemite Coil which was used by players at the time the game was still widely popular so that they could develop their Join Avenue as fast as possible (thus ignoring the game progression part for in-game fans).
Best Answer
The moves you teach it may largely depend on what ability your Skitty has;
Normalize
This ability will give all of Skitty's attacks Same-type attack bonus, so priority moves like Sucker Punch (must be bred in) can get a little extra power behind their speed. It will also let Skitty use moves like Thunder Wave (TM73) on the otherwise immune ground types.
A downside to normalize is that ghost types will be immune to all your direct damage - this can be mitigated using Foresight (learned at lvl4). Additionally, Rock and Steel types will be highly resistant to your attacks.
Cute Charm or Wonder Skin (hidden ability)
Zen Headbutt (must be bred in) is a good counter to normal types' greatest weakness - fighting. High priority moves like the previously mentioned Sucker Punch or Fake Out (move relearner) are still a good choice.
Skitty can also learn Baton Pass and Wish though breeding - combined with Calm Mind (TM04), this can make for a fairly decent support (combine those three with a special attack like Ice Beam (TM13) or Thunderbolt (TM24) to let skitty take advantage of its own stat boosts.
Smogon University goes into further details on specific builds, giving suggested EVs, natures, and items as well as strategies. You can copy those movesets to the letter, or modify them to your liking.
EDIT: If you are looking solely to teach moves to an existing Skitty, and not do any fancy breeding;
And if this is just against the NPC's throughout the story, always remember that there's nothing a little back-tracking and grinding out a few levels won't cure.