Hi OP
The gain control is varying the tube's circuit gain. The volume control varies the level of the input signal. They are completely different animals.
You can just put the gain control at some random point like 3:00, but is that the optimal point? Not clear. One would need to know a lot about the circuit design to make that call. I'm not surprised AI isn't getting involved in the answer, as it can be quite complicated. It's also why few amplifiers actually have gain controls (except for vintage ones, and that was because of the wide variety of speaker efficiencies back then).
My suggestion is that you try a range of settings. There is likely to be one spot you prefer for a 'given volume level.' Most gain circuits have a sweet spot. It will still work outside of that range (since they made it available to you to adjust) but it won't necessarily work as well (e.g., less linear).
What I do is listen one night with it turned all the way up. Then the next listening session, turn it most of the way down. Use the volume control to set the music at about the same level for both sessions. Then try turning it to the midpoint, then vary from there, etc. Trying the two extremes first will help you "frame" a reference point to fine tune the setting. My MC240 clearly sounds its best between 1:30 and 2:00, but your results could be completely different.