The best program to learn is Inkscape, it's free and open source. It's the vector graphics program I use to make my artworks, 'cause my scanner doesn't support Windows 7, so I can't make traditional artworks on paper. If you'll have any kind of question about it, I can always help you (at least I can try, since I never tested my skills at teaching things, lol!)
That one, coupled with Photoshop (or GIMP), make a very good mix for digital art.
~~~ Quote by kadeathnas: yes, i hope to learn soon ^^ ~~~ The best program to learn is Inksca