After scrounging a free sample of ceramic wool I read the MSDS, looked up the insulation properties and went with Home Depot aluminum backed fiberglass. I peeled the insulation down to ~3/4" since that's about all the room there is.
I used aluminum tape for gas appliance exhausts to fix the fiberglass in place.
What's this thing?

I also (partially) insulated the group boiler. I wrapped the front part of the boiler as well, being it is easily removable should I rethink and decide I don't want glass up there. For now I've sealed between the group head and the insulation with aluminum tape.
I insulated the top of the boiler by cutting fiberglass squares and nesting them between the various gizmos.

There still seems to be plenty of heat loss to the cup warmer. The heaters kick in less often now but I didn't do any "before" timing.