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Inflate them to maximum pressure, although this will cause a very harsh ride and poor handling if you don't haul a load.
Max sidewall pressure is unlikely to make much mpg difference. Consult posts/threads here and elsewhere by CapriRacer, a tire engineer. The trade-off in handling, braking and tire life won't justify a miniscule FE gain. Percentage pressure rise once at op temp (steady state for about an hour or more) is more important to establish best psi (which is always against actual load).
This truck got 120k on the first set of tires. And that was at factory recommended 50-psi FF and 50-psi RR. Brakes lasted just as long. Consider all this carefully, as "major" changes generally have a cost associated with them.
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