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There's a lot of biology involved that I don't understand the intricacies of, but basically the more time and at more depth you are underwater the more your body is dealing with changes in the density and makeup of your blood. You need time on the surface to normalize. For a similar reason you need to do safety stops to allow your body to adjust to the changes.
For normal recreation dives, it's pretty simple that people are limited to (IIRC) two dives/two hours per day as a general guideline. Once you get into deeper dives, using different breathing mixes, and other stuff people have to start doing a little bit of double checking to make sure they don't overdo it.