Yeah the concept of a master volume seems to boggle peoples minds. All my friends that are guitar players seem to think that cranking the MV pot, but putting the channel volumes low, is essentially pushing the power amp to it's full potential while keeping volumes low. It's tough to get them to understand what the MV actually is. As winter snow has said, it's just another leveling pot after the tonestack to help balance channel volumes.
Post PI masters are slightly different, but you rarely see those in the amps we use anyway.