Currently players are not able to buy multiple amount of the same item from the vendor at once. Instead you are forced to buy them one by one.
This has been reported as an issue in official forums with a lot of players complaining about it, so it's probably going to change in the future, and once it does i will update my answer.
As of Version 0.10.2b you can now use Ctrl + Click to buy items from vendors.
tl;dr: Items that people want to have are expensive, other items are not. I suggest using a service like poe.xyz.is to get a feeling for the value of an item you might want to sell. Especially for uniques it can give you a very good idea of an item's value.
This is a pretty open-ended question so a conclusive answer may be hard to come by. That said...
Affixes come in different brackets, or tiers. For example, % Increased Physical Damage comes in 7 tiers ranging from "Heavy" (+20..49% IPD) to "Tyrannical" (+150..169% IPD). The stronger brackets are of course more valuable, while the weaker ones may even reduce the value of an items since they prevent stronger ones from spawning.
Movement speed is incredibly important on boots since it cannot spawn on other gear, and it's rare to see a pair without MS sell at all, let alone fetching a high price.
Affixes that align well with the base item type are more expensive. E.g. Increased Critical Strike Chance is much better on a Dagger than it is on a Maul, because Daggers already have a high base crit chance and are therefore commonly used in crit builds, while Mauls are strength-aligned and often used by characters who cannot crit due to Resolute Technique.
Affixes that align well with each other can increase the value of an item - or rather, affixes that don't align can relegate an item to the vendors. A combination like % Increased Physical Damage and flat Increased Physical Damage, or +2 to Fire gems and +1 to all gems can get quite expensive, while no build I know of makes good use of both Attack Speed and Cast Speed. Especially on base types with a large mod pool (e.g. jewellery, daggers, wands, sceptres, staves) having well-aligned affixes can increase the value dramatically.
Resistances are pretty popular on socket-less items because they're easier to swap around to accommodate changes in your other gear.
With the release of Forsaken Masters, a 5-affix item may well be more valuable than that same item with a 'decent' 6th affix, because it leaves some room for the buyer to customize the item.
Corrupted items are in general less valuable than their non-corrupted variants because the sockets are locked, but if they rolled a very good corruption this is of course not the case.
It could be said that different factors have multiplicative scaling - e.g. a 6L item is expensive, and an item with good affixes is expensive, but a 6L item with good affixes will not simply be twice as expensive - it will cost you three and a half fortunes.
Best Answer
I do not believe that Orbs of Fusing are able to give you a completely unlinked item, but there is still a way to get it.
1.Use orbs of fusing until the top two sockets are not linked.
2.Using the crafting bench, craft 2 sockets onto the item. Your item should now be two unlinked sockets.
3.Craft the item back up to the amount of sockets you want. Sockets gained in this fashion should always be unlinked.
Keep in mind that an item with 5 sockets already 5 linked, or 6 sockets already 6 linked, cannot have their links undone with a fusing orb. Drop the item down to 3 sockets with the bench first, then you can start using fusings.