2D Paint packages

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Frankly, if you can afford them, the pro tools are hard to beat:
Photoshop 6/7 (preferably with Illustrator or Freehand as well)

I find a good 3d modeller/renderer indispensable for creating 2d graphics these days. Usually I use 3D Studio Max, but Carrara, Strata, Amapi, etc. are far cheaper (and probably easier to use).

Paintshop Pro is a poor relation to Photoshop as an image-processing application, but its pixel pushing tools are ok.

For actual pixel pushing (where anti-aliasing is actually annoying rather than helpful) I love Studio/32 -- although it doesn't run well under OS X. (Studio/32 is a Mac program by the folks who did DeluxePaint -- except it was fully 32-bit with alpha channel support.) The lack of really good pixel pushing tools today is quite disheartening, most of the programs I see today don't "get it". Studio/32 and DeluxePaint had awesome keyboard controls and incredibly powerful masking tools.