I reckon you're
'over thinking the problem', if indeed there is one.
Does the vehicle sit well, is the rear sagging with normal load/use and with say 5 psi in the polyairs ? If so all OK so far.
With the vehicle loaded and 25 psi in the poly airs does the vehicle still sit and drive OK ? If so you haven't got a problem so why all the worry ?
Don't even think about 100 psi in your polyairs

, you are correct that 25 psi is tops.
Another benefit with your polyairs is that as load increases and the springs compress, say when driving over rough ground, the polyairs become harder to compress with load giving a 'variable rate' effect. This means you don't bottom out and the strain/load on the vehicle its occupants and suspension is minimised.
Do you have std. springs ? It is important to have the correct length of polyair for the springs fitted. There should be little or no space above/below the airbag with the vehicle unloaded, a plastic spacer is often installed under the airbag to achieve this.
With quality heavy duty shockers I reckon you could be good to go with what you've got.
Deano

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