Well, it shouldn't be /too/ hard. You just need to look online for some custom brushes or try to make one using Photoshop's available tools.
The most basic way is to cut out your character using the Lasso Tool, and work around that.
Some examples of what I mean:
(taken from photoshop itself, cause it won't damn export properly. Which is why you see the transparent background..
Try looking for a theme for your character, and again, go from there. Some screenshots you can take from in-game prove really good.
Practice gives good results when you put the effort into it!