Do a little reading and you'll see a lot of your questions have been answered already on here in a lot of detail. For chest you basically have 2 types of exercises: presses and flyes. Presses are your bread and butter chest exercise. Flyes are seen as more of an isolation movement for detail and definition but I'm absolutely convinced they can build decent mass too. (There are also cable crossovers and pullover exercises which you can add to your chest workout for some variety and detail work.)
Bottom line: do both. I typically do presses first and flyes toward the end of my workout.
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