For the beginner, the CMCK really is a good resource. The trickiest thing for beginners is often the cutting out, getting a clean image to play with, cutting out and finding components for your vision.
Once you have some confidence you can start to alter the figures, add or change arms, hands, faces. Add nails, ropes, change backgrounds, etc. You can start to blend the components together better, to make a cohesive picture. Or add filters or special effects for a more artistic touch.
It really is a matter of jumping in and trying, and asking questions. Look at Wragg, he was a complete novice a short time ago and now he is producing a very interesting illustrated story.
http://www.cruxforums.com/xf/threads/dux-rebellium.6844/
Software? I use Paint Shop Pro, I think Madi does too. The market leader of course is Photoshop, but there are others out there. Make sure you get something that allows multiple layers!