TL;DR - thanks to the huge pre-drive highs boost from "bite", highs are the first to saturate and be limited as signal levels hitting drive, or drive itself increases. Full post below:
Alright, I just got back from rehearsal, and figured following up on my post above might be a nice way to unwind for the night.
Back on the topic of pre- and post-drive EQ, see below for a graphic that illustrates the concept as it pertains to VT units and the substantial pre-drive highs-boost from "bite" when engaged (or by default on units without the option). This might be a no-brainer for some as it's pretty logical, but I was still interested in seeing it with my own eyes to better understand what's going on.
The plot shows how the drive circuit saturates/limits/distorts frequencies boosted by "bite", starting with green which is the least saturated signal, to orange which is slightly distorted, on down to blue which would be significantly distorted. Since bite is such an enormous pre-drive boost, those frequencies are the first to saturate.
The change in signal could come from either increasing drive, or from increasing the strength of the signal hitting the drive circuit. Again, this might seem obvious, but what this means is that harder/softer playing has the same effect, as does note decay. The difference between the green and orange sweeps is just a 2dBu increase in amplitude for each increment with no changes made to the pedal. This is easily all within the realm of typical playing dynamics, and even changes between the attack and decay of a single note.
Note: levels have been adjusted to show the relative change in highs. In reality, for each 2dBu adjustment, the entire curve would shift 2dB as you'd expect. Also, as a brief disclaimer, these frequency sweeps tend to not tell the whole story, as generally those saturated frequencies create additional harmonic content above the point of saturation - but given the steep roll-off that the speaker sim imparts, much of those higher harmonics are drastically limited.
For reference, this is how I had my VTDI dialed in when I ran the sweeps above. I'd characterize the yellow line to be relatively equal to that of a note with a hard attack from my Precision.