Best take a look aat the accuracy of the boiler gauge and the relief valve; most relief valves in residential hot water systems are rated at 30 psig, so some replacement might be required.
You seem to be doing the purging correctly; but being able to purge at 25 psig might do the trick. As you have to drain the boiler to install a new gauge and/or relief valve; that would be a good time to sweat in a baseboard tee at the highest point in the circuit so you could install a manual air vent.
www.heatpro.info heat/cool right-sizing
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