Photoshop doesn't do vector graphics either.

Vector graphics is entirely different from messing around with bitmaps, it doesn't make sense realy to mix the two.
You use a limited bit to make masks and such, but if you want a free program to do vector graphics check out inkscape.
Right now I use for FREE (as in freedom, open source, free software type things) are
Gimp = bitmap/image manipulation.
Inkscape = vector graphics
Scribus = Desktop publishing/layout program (like what quark express is for)
Blender = 3-d modeling
POV-ray = raytracer
And there are a few other besides
that, but those are the best so far that I am aware of. The most professional of them, I mean.
I don't know of a realy good painting program. I considur Gimp and Photoshop to be image manipulation more so then image creation. Stuff like Fractal Painter is completely different, IMO. You can do some painting in Photoshop and Gimp, but I don't like to do that. It's like using Photoshop or Illistrator to do layout work(pain in the rear). The fonts always looked screwed up, it takes to much work to do simple stuff, it's just not worth it. So that's how I feel about painting in Gimp/Photoshop, too.
I would realy like to find a good free (as in FLOSS) that can do painting well.