Someone asked a question about the process of painting a character, so I'll take a stab at that one. There are many processes that each have their strengths, but for the sake of learning this is what I'd suggest. This process is based around the way 3d rendering programs work, using separate passes and combining them together for the final effect. Separating the processes in this way helps you think through what needs to be done.
First of all, start with a sketch. Don't try to design a character as you paint, unless you are really advanced and probably not even then. Inked line art is fine.