You use the volume to set the appropriate preamp gain staging, use boost to hit the rails, and use the master to control the overall output.
The Boost stage is a FET that is designed to emulate a pushed tube. Adjusting either the Volume or Boost will effect the level at the FET. If the signal entering the FET is hot enough the circuit will compress. An even hotter signal will cause the circuit to break into drive.
Although people may call pushing the Boost circuit into drive territory hitting the rails, that is not correct. The rails are the + and - DC power supply lines. Hitting the rails occurs when the signal swing in the output section approaches the voltage of the power supply rails and can go no higher. In other words it only occurs when the output section is pushed beyond it's limits.
To set the input level we assume one would turn up the Volume until distortion occurs in the preamp and/or tone stack. IME the resulting distorting tends to come on quickly and is harsh. Most consider it undesirable. So the normal process is to back the Volume of just a touch so the signal passing through the preamp and tone stack to the Boost circuit is always clean.
The 800RB I used had some problems with signal to noise ratio. So it was necessary to adjust the Volume, Boost, and Master to keep the hiss as low as possible. In other words, I wasn't able to simply turn up of the Volume till distortion occurred and then back it down a hair. Instead the ideal setting varied with how the tone controls were adjusted.
Here is the block diagram of the 800RB. Adjusting the Volume effects the signal at all points after the Volume control. Adjusting the Boost Control effects the signal at all points after the Boost Control
The Boost switch is drawn is not accurately. Here is the actual schematic of the Boost circuit.
There may be some variation of different production runs of the amp. The Boost switch is connected to A. The switch toggles a Relay (U5). In one position the signal is taken off the bottom of the Boost control (R82) at pin 4 of U5. I.E. the signal is dropped by the entire 50K resistance of the Boost control. In the other position, the signal is taken off the wiper of the Boost control at pin 5 of U5, so the resistance seen by the signal is variable from ~0 ohms to ~50K.
J113 is the FET.