I know that while springer models are not good at predicting springer performance without calibration data, they are not usually too bad at assessing the effects of changes. Years ago when I was keen, I created a complex springer model which did seem able to make a reasonable estimate of the effects of changes to a calibrated model (based on a lot of your data, Jim). From what I remember, energy increased slightly when start pressure was reduced from some of the high values, everything else being kept constant. There did come a point where the trend reversed, but at a very low pressure. The reason seemed to be, as Jim says, that at lower start pressures the piston and pellet are going in the same direction for longer, though it would also depend on the barrel length how big an advantage there is.There is also the problem in that the pressure seen by a pellet is a dynamic pressure, and most metals will withstand a much higher dynamic pressure than they will a static pressure. Hence, the rate of increase of pressure may also be a factor in when the pellet starts.
You can buy a used copy of from trigger to target for lots of money; or you can download a copy for free. If one owes the Cardew estate a royalty, how would that be paid? $92.11: www.amazon.com/Airgun-Trigger-Target-Gerard-Michael/dp/0950510823/$129.95: https://www.ebay.com/itm/185351239869?http://www.mediafire.com/file/5mcemcyutrm/The_Air_Gun_From_Trigger_To_Muzzle_s.pdf/file
Pellets transitioning from the lead-in to the rifle bore ARE a "pressure buildup dump valve" in it's simplest and IMO most elegant form.
In “The Airgun from Trigger to Target”, pg 12, they show an ocilliscope trace that shows the pellet starting to move at a point very close to the peak pressure in the gun. At a different part in the book, they figure the max pressure between 1300 and 1400 psi. Your quest for a pressure relief valve might be an exercise in futility.