Well, chalk this up to another case of "had to manually re-set options for them to take".
After manually re-setting every voltage indicator, the problem was corrected.
I am now testing 4.20GHz using LLC 5, and 1.225V (BIOS setting, which reads 1.245V in the "Current MIT Status" screen). Under the same parameters, in Windows, 1.24~1.26v is read in TouchBIOS (but has stabilized at 1.24V after 5 minutes in Prime95).
So far, temps are getting to 68C (core1/2/3/4/package readouts currently read 63/66/66/61/68 respectively). (Room temp is 29.4C (85F) right now.)
At 4.0GHz (1.21~1.22v, LLC5), with the same ambient room temp (29.4C), I usually saw 61/64/64/60/65C, so I am wondering if the extra ~3C (and 0.05v) for only +200MHz is really worth it... So I might need a better heatsink or at least fan (the Arctic Freezer Extreme rev 2's fan runs at about 1000RPM and is custom-fitted for the HSU).