If you unlock a Zer0 Skin, while playing Maya, Zer0 will have that skin available in the Quick Change station on the same profile.
EDIT: Note that certain Heads and Skins, in particular the Community Day heads and skins, are account bound and will disappear if not used before quitting BL2. I am not sure if they still drop, but if they do you need to “use it or lose it”. I found that out the hard way (a while ago), when I found one of the Krieg Community day items and stored it in Claptrap’s stash. It was gone the next time I loaded BL2.
VaultHunter101
(So long, and thanks for all the fish)
#3
Yes, all skins and heads are associated with your profile, not a particular character save associated with that profile. You do have to “use” them from within your inventory before they’ll show up for the relevant character at a quick change station, though. Wish I’d known this when I started, as I dropped or sold a lot of skins/heads when I realised they weren’t for the character I was playing.