Overhead, clipping etc.
Here's an example.
I can set my gain all the way up, so that when I hit volume 10 of 62, I am at the amp's full power. Anything above 10 would push the amp into clipping, and therefore fry components. But, as long as I don't push the volume knob past 10, I won't blow anything up.
But, if I set the gain to hit the max voltage at volume 45 of 62, I have much more room to play with. Another reason is to avoid deck limitations. Sometimes decks will distort the signal earlier than others. A rule of thumb for those new to audio, is to set your amp so that it hits maximum desired voltage at 75% of your decks power. This way you avoid clipping, but if there is music recorded at a quieter volume, you can push the knob a tiny bit past 45 to make up for the low volume recording.
Ultimately, you can set the amp to volume gains at wherever you feel, as long as you use a DMM and make sure not to drive your amp into clipping by going over your own pre-set volume limit.