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Illustrator & Painter are used for different things. A basic graphics
software suit might include Illustrator or Freehand (the two dominant draw
vector programs) & Photoshop. Painter is a supplemental program that allows
more elaborate paint effects, but less powerful compositing features than
Photoshop. A good professional designer would probably use both, but it is
hardly necessary to teach both. If you can comfortably find your way around
Photoshop, Painter will seem natural.
Cheers!
Jim