I'm pretty much on the same page with @Devin, SAI for lines and PS for coloring.
I feel like if you're not used to digital art, MS5 is a pretty good place to start. It smooths out your lines and adds more line weight and variation on its own (more so than SAI).
I've noticed a lot of animators recommending coral painter - but the user interface is a disaster.
I just got my hands on z-brush, going to try my hand at 3-d modeling for reference purposes, but we'll see how that goes.
Oh, and I think for first time digital artists, SketchBookExpress is decent - it's not nearly as robust as the other programs but it's free and pretty self intuitive. I haven't tried the Pro version, but looking at screen caps, I think it's better to just get Manga Studio for like $30.