The ENVE numbers would be fine if they were specific to a rough surface. Yes, the width of the ENVE rim tire well plays a factor in lower pressures, increasing volume in the tire and making it behave as a tire of larger width... the thing to remember though is that the tire doesn't gain all the radial height that you would get from the wider tire.. so while you can make a 25mm tire 28mm wide, your rim edge will be ~2mm closer to the ground that it would be on a 28mm tire on a slightly narrower rim..
Having said that, look at the charts in our blog, those are actual measured values on various surfaces and you can see that the difference in road surface roughness is a major factor. Similarly, rider system weight is a big player.. so you can't just go off of rider weight, but need rider+ bike.. and also need weight distribution front/rear.
I typically tell people to pick a starting point and drop pressure from there, but if you are on the ENVE chart, I'd start there and go up a bit.
As an additional data point, I'm 175lbs and ride a 21lb steel road bike with 28mm Corsa G+ on 17.5mm inner width 303's. Tires measure 30.1mm and my optimal setup is 66/68psi front rear while their chart would have me at 56-57psi.. which is a fine pressure, but is well below optimal based on our testing on crappy Indiana roads... on nicer or newer roads the delta would be greater still as my optimal pressure would be greater than the 66/68
I'd suggest listening to our podcast to learn more here, but the real way to do this is to keep a log and test it for yourself on your riding surfaces. We do this with all of our pro teams and athletes and it is invaluable to keep that log so you can go somewhere new, and say 'this looks similar to X' and then you have a solid starting point for you, and your setup.
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