A pull-up is going to work your lats and biceps.
The bench press is going to work the pecs and triceps.
As a general rule, pushing exercises will involve the triceps in some way.
Pulling exercises will work the biceps in some way.
The only exceptions are flys, which is performed with straight arms.
As far as the pull-up goes, it will work your back no matter which way you hold the bar. You can do a pull-up with the reverse motion of a bench press or having your elbows facing forward and pulling up.
Don't concern yourself with "best" exercises, just worry about doing these exercises correctly. Master one or two exercises before you try others.
I take it that you are young which means that you really need to create a good foundation. Good form now leads to good form later. Bad form now will lead you into nagging injuries and poor results.