While you're correct, all you'd be checking is that your calibration is correct and your computer is still multiplying X * Y to give you PPO2. I can't think of a single thing checking mV underwater will tell you that the PPO2 display won't tell you.
I was referring to your scenario of Calibration -> Dive 1 -> Calibration ->Dive 2.
In that case, what you would be checking is how that factor changed, i.e. how your cell output changed at standard conditions, which is what "calibration" uses to generate that factor. The relevance would be that wet recalibration can potentially mask a very large dropoff in output, which may or may not be relevant in predicting failure. On the other hand, as you pointed out, what you really want to calibrate for is real world conditions, which change over the course of a dive.
The alternative way of getting that information (i.e. the change in the factor between dives) is what you suggest, flushing with dil or O2 at a known depth, and then comparing that from dive 1 to dive 2. As discussed upthread, that depends on (1) a perfect flush (at least in the area where the cells are), and (2) and accurate depth reading. A better way is using the pressure pot, assuming that the idiot who bought it didn't blow the head off and potentially damage the gauge.
