lokiju: So does a character with Bluff have to be the one to talk to an NPC for a bluff option, or is it factored in party-wise? As in, does the AI check the highest score of all characters, or does the specific character with, say, Appraisal, have to be the one to talk to the NPC to get the best prices?
Only the character doing the talking matters. You can tell by hitting the log book and seeing who gets credit for bluffing, gathering info, using diplomacy, etc.
So make sure you have a smooth operator in your party. Bards are good candidates. This is a character who should have high Charisma (for the bonuses) as well as high Intelligence (for the extra skill points). A lot of dialog options are only open to a person with the proper skills. Btw, Diplomacy is probably the most important one of them.