The new valve stopped the leak and I was able to run a serious descaling and deep cleaning of several parts. The boiler safety valve I cleaned looks like it should work (and maybe it is). The part looks like this:
Mine is clean, the spring looks good, and the seal looks good so I think the problem is somewhere else but this spits out a blast of steam when I load the portafilter to pull a shot. I get a small stream for maybe 5 - 10 seconds and then the safety valve releases. I tried grinding coarser (but not all the way to drip) and it does make espresso come out at first. The pump puts out 110 mL in 10 seconds with an empty portafilter in the group.
The pressurestat is a Mater and does have an adjustment screw. The piping leading from the boiler to this part is very clean now as well. If anyone has an idea of what might need adjusting/cleaning/or replacing I would really appreciate the help.
The valve shown (popoff or safety valve) should not be adjusted. It's supposed to be set to open if boiler pressure exceeds 1.8 bar. It has nothing to do with group pressure, so pulling a shot will not cause it to open.
I'd use a digital thermometer with a thermocouple on the boiler to monitor boiler temps, which for HX boilers should be in the 251 - 254 degree range. IIRC, Adjust the pstat CW to raise & CCW to lower (I think this is correct, but pstats vary so check for directional arrows near the adjustment screw).
The popoff should be set to open at ~1.8 bar, which is just under 270° (again - IIRC?) If you adjust the pstat higher you can use the digital thermometer to see if the popoff is opening at the correct temp, and if not replace it.