You could probably do something along the lines of a script adding you to a faction once you don that armour. The Forsworn, for example. I did this for my own game in Oblivion, Fallout 3, and Fallout NV but I haven't really looked into it in Skyrim. The whole script savegame embeding thing has put me off somewhat. I'm a little surprised that no-one seems to have taken this on as a mod as yet.
The most I've done was tweak some NPC responses to what the PC is wearing, like guards telling you that you're wearing brigands armour when you're wearing bandit/thief armours etc. And wearing some of the skimpy outfits will bring comments about how cold you must be, how what you're wearing won't be any good in a real fight, or to go put some clothes on. Small things amuse me.
