I finally figured out how the Pen tool works with Shape Layers, and how to use the Convert Point tool, but I still have some logistical things I gotta work out.
Anyways, this is a character from Full Metal Alchemist... my buddy likes the show so I did it for him.
Original:

Vector with black/white background:

Vector with transparent background:

I'm pleased that I don't have holes when it comes to the background showing through, like I did last time, but I still have a hard time figuring out what should go on top of what, so there are overlay issues.
Again--and still--any suggestions would be great.
Note: I would have blown up the vector, but I rasterized some layers without realizing I'd lose the ability to enlarge without losing detail. >_<
me = nub