The most effective exercises for bust enhancement would basically be anything that is going to work your chest muscles.
You can only build up the muscle underneath the bust - these exercises won't increase the actual size of the bust. There are two major categories of exercises - ones that will build and ones that will help define.
Exercises that will help with definition include Cable Cross-Overs, Dumbbell Flyes (flat, incline or decline) and the Pec Deck.
I would recommend using primarily exercises that build up the muscle, while including the exercises from the second category in a smaller ratio. I would say for every 3 sets of building exercises, do 1 set of defining exercises.
Most women tend to do the complete opposite, choosing the pec deck and cross-overs because they're easier and neglecting the presses. You'll get better results by working at the exercises that are harder.
The best bench press version to use to enhance the bustline is the decline bench press. This exercise is done on a decline bench, so your head will be lower than your feet. This position tends to emphasize the lower chest muscles.
Building this area up will push forward what you've already got, helping to enhance the bust area.
These exercises will pull your shoulders back, keeping you from slouching forward. Improving your posture will probably do just as much for bust enhancement as will working the chest muscles.
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