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Your arms should be positioned perpendicular to the bar, shoulder length apart.

Bench pressing is a chest workout. If you keep your arms positioned shoulder length apart, you will be working your chest. If you move your arms inward more, you will be using more of your triceps rather than your chest.

An incline bench press will help with your upper chest, and decline bench press will help with your lower chest.

Hope this helps!

There are different places that you can put your hands to work different muscle groups while bench pressing, usually you want your hands to be a little past shoulder width for normal bench pressing. The major muscles worked while benching are your pecs and triceps, and then your back muscles are slightly worked also. If you place your hands closer together then you can focus more on your triceps.