You really have to know electronics and look at the amp schematic to understand this stuff. Whether it matters will depend on where the distortion is generated in the circuit and what sound you want to get. If you’re not an electronics guy, probably your best bet is to play all the candidates at the volume you want to use and see what you like best. Failing that, take the advice of someone you trust.
If you’re interested in the electronics, here’s a shortish and yet still oversimplified summary:
Guitar pickups generate tiny signals, both in voltage and current. Tube amps generally have preamps designed as voltage amplifiers to boost the voltage a lot and the boost current a little (and do tone shaping). This signal feeds the power amp, which is designed as a current amplifier to boost the voltage a little and boost the current a lot (so it can physically move the speakers magnets).
Most modern power amps are push-pull configuration, which means that one set of tubes handles the positive voltage swings, and another set of tubes handles the negative voltages swings. This means that each set of tubes can idle at ground voltage, and use power in little sips so they don’t consume a lot of current and thus age more slowly. In order to separate the positive swings from the negative swings, we need an extra tube stage between the preamp and the power amp. This is called the phase inverter, and it feeds the positive swings to one set of output tubes, and inverts the negative swings before sending them to the second set of output tubes. The two sets of power tubes feed opposite ends of the output transformer, so the inverted negative signal gets inverted again and the negative swings are restored.
Distortion can be generated in the preamp tubes, in the power amp tubes, and in the phase inverter tube (as well as in other places like the output transformer, even in the caps and resistors). Every amp design will have different proportions of distortion from these stages, and it will vary by volume. Generally, the harder you push any particular stage the more it will distort.
A master volume turns down the input to the power amp, which will reduce the distortion from the power tubes. If the master volume comes before the phase inverter, then the distortion from the phase inverter will be reduced when you turn down the MV. If the distortion from the phase-inverter is part of the sound you want, you will usually want the master volume to come after this stage. Whether that’s true depends on the design of the amp and your personal tastes.
Some smaller amplifiers (generally 10 Watts or less), like the Fender Champ and many of it’s descendants (Vox AC4TV, Epiphone Valve Jr., Garnet Herzog, Kustom Defender, etc.) are single-ended, that means that a single set of power tubes handles the positive and negative swings together. To make this happen, the tubes have to be fully powered at all times so that the idle voltage is about halfway between ground and the supply voltage. So they burn up power tubes more quickly, but they don’t require phase inverter stages, so there’s only one place to put the master volume.
Since power amp distortion is part of the signature sound of some amplifiers (older Marshalls, etc.) some people dislike this approach, and prefer to use load boxes or reamping to push the power tubes hard but still get lower volume. Many Fender amps, especially the Twin Reverb, generate very little distortion in the preamp and phase inverter stage, and have to be cranked to ungodly volume levels to generate power amp distortion. (Personally, I love this sound, but it tends to kill small animals nearby.)
To decouple the volume from the amount of distortion, many modern amplifiers (especially solid state amps) generate the majority of the distortion on the preamp. Preamp distortion is generally though of as harsher and fizzier than power amp distortion, but amp makers work very hard at tone shaping, so this depends a lot on the amp and on your preferences.
Power scaling is a newer approach that allows you to reduce the headroom in the power amp so that it distorts at lower volumes. This allows you to get power tube distortion at low volumes without reamping. I think it sounds very good, personally, but it doesn’t come standard on many amps. It’s usually either expensive to buy stock, or requires you to mod to an existing amp. It also doesn’t capture the distortion you get from pushing speakers really hard, which some people care about a lot.
Having read all that, if you want to know whether the MV in a particular amp is a PPIMV, you would look at a schematic, identify the different stages and see whether the MV is between the preamp and phase inverter, or between the phase inverter and the power tubes. Again, how much this matters depends an awful lot on both the amplifier in question and on your personal tastes, so using your ear can save you a lot of time and trouble here.
Sorry for the dissertation. Hope it helps somebody.