As someone who has debugged his fair share of tricky low-level issues, the parts that I find impressive in his blog posts are things such as "then we look at the bytes in memory and oh yeah, this looks like an exception record". I would usually not think to do that (or be able to recognise it as easily as I presume he did).
I assume it's mostly just something you learn to recognize after decades of poking at the same things. I remember being impressed with Thiago (Qt developer) being able to immediately tell if a pointer was heap allocated, invalid/unaligned, etc. until I spent more time poring over /proc/*/maps and in gdb. Never figured out how he could tell someone's Qt version just from an strace excerpt, though.