My split is: Monday: Pecs/Back/abs, Wednesday: Legs/Calves/abs, Friday: Shoulders/Arms/abs.
I do mostly compound lifts (ie: squat, bench, deads, upright rows, clean and press etc). So with overlap, most muscles are getting hit more than once a week. I find it very hard to eat on days I train. My body just feels too hyped up. I use my off days to rest and eat like a horse, perhaps do some light cardio and or active recovery.
This is just what works for *me*. I suggest a trip to the training board where you will find some great information such as the 5x5 program by Madcow and some wonderful training journals that have tons of great real world info.
As for being/becoming Mr. Olympia or an IFBB pro, only your genetics, drive and determination will allow that to happen. You have to have it all. Not even the genetics alone won't do the trick if you don't have the will and desire to be one. And trust me, if you were meant to be a Pro or top level NPC athlete, you will know soon enough with a little bit of proper training and nutrition.
In the end, find what works best for *you* and strive to be the best *you* possible. That's all any of us can do. The rest is up to fate and what genetics we were lucky (or in some cases unlucky) enough to be born with. Good luck with which ever program you end up doing.