If you wanted to add a master, then add it right before the PI coupling cap. You will have to add a coupling cap before it though after V3a plate. I.e. the coupling cap from v3a isolates DC geting to the master pot, and the coupling cap on the PI prevents the zero DC on the master volume pot from messing with the bias of the PI.
Lets see,
Your first gain stage will bump up the signal about 40 times. Lets say from 200mV to 8V pk.
Your tone stack (without a CF) will cut the signal about 1/3, so from 8V down to 2.6V pk.
On your next gain stage at 100% volume, gain will be again 40 times, so we are back up to 104V pk. BUT really its going to hit its limits, so lets say around 60V pk. This stage is the start of your preamp distortion.
Then we hit the 3.3M resistor. This will drop the gain a lot about 70times, so your signal is back down to 0.85V pk.
Now into v1b about a 40x gain, so signal is up to 34V.
If your master was on 100% - or you had no master at all, you would be cramming 34V into the PI. On a clean swing the PI could probably handle 2V pk before some kind of distortion starts to happen, which is OK, the PI is used for distortion on a lot of circuits.
So looking at it this way, a master would be a good thing to help you get more clean out of the amp. You also have two places for distortion: V1b and the PI. My suggestion, once you have this built, is to replace the 3.3M drop resistor with, say a 50% voltage divider. This will give you a lot more signal into V3a and help you shape more distortion on the other side of the wave. By adjusting the plate and cathode resistors on V1b and V3a you could really get lots of saturation or lots of hard clipping distortion on both sides of the wave. Anwyays, food for thought.