You can create a full-featured skin using just MSPaint, too, except for the per-pixel "glass" effects. I agree with Scarebear - a good way to get started (what I did) is to load up a skin in SkinStudio (I actually started with Notepad before SKS was published, but that's another story) & start looking at all the graphics & attribute parameters, playing around with them & reloading the skin to see the effects of changes (SKS Preview is good for most things but doesn't preview a number of features).
And DO budget a lot of time for it - it's both challenging & addictive.
Cheers,
Daiwa