First thing we do is ask what the house is doing, not what part someone thinks is bad. Is the burner firing at all? Does it fire and shut off after ten minutes? Are some radiators hot and others cold? In a lot of Warren two story homes the answer is warm downstairs and cold bedrooms, and that pattern points somewhere very different from a boiler that won't light.
If the burner is lighting, we watch a full cycle at the gauge and the pressuretrol. A pressuretrol cranked to 5 or 10 psi by the last guy doesn't push more heat upstairs. It just shuts the burner off on pressure before the far radiators fill. We pull the pigtail and check it for sludge, then we follow each steam main to the end and look at the main vent.
A main vent that's clogged or missing, or a little radiator vent screwed on where a main vent belongs, means air stays trapped in the pipe and steam can't get past it. Air has to get out for steam to get in. We feel along the main: hot up to a point and cold after it tells us exactly where the air is stuck.
If the burner won't light, we go through the sequence in order: thermostat call, 24 volts at the controls, the low water cutoff, the pressuretrol contacts, then the ignition side, whether that's a thermocouple, flame sensor or hot surface igniter. We teach the homeowner one easy test before we go: set the thermostat a few degrees above room temperature and listen for the burner to start.