why not both?
some amps are clean-only, they're best used when the gain is just sub-clipping.
some amps have lots of grit, so if you need cleanest sound, you max up the master volume and then use the gain as the volume.
some amps (and desired tones) are in between, so use your ears.
at the end the proper way to set your amp should be written in your amp's manual. other amps might have it differently.
some amps are clean-only, they're best used when the gain is just sub-clipping.
some amps have lots of grit, so if you need cleanest sound, you max up the master volume and then use the gain as the volume.
some amps (and desired tones) are in between, so use your ears.
at the end the proper way to set your amp should be written in your amp's manual. other amps might have it differently.