One of the giant money sucks is when your local MX tells you a cylinder failed a compression test, and tosses you a $3k estimate to replace the cylinder, but then doesn't know how to lap a valve or do a solvent purge (to clean/unstick a ring) with the cylinder in place.
Conti lower ends are super solid, but their valves...ah, leave something to be desired. You can get a cheapo borescope that takes awesome pictures with your iPhone right off Amazon. Pull a plug and take a peek every 100 hours. If you see anything other than a circle on the exhaust value, lap the valve, check the rotator, and you'll save yourself some drama.
When I had my airplane, I did stock some parts in my "AOG bag" in the baggage compartment, namely a spare mag, a starter relay (could double as a battery relay), spare tire valve cores, tow pin and a spare data card (in case one got corrupted on the road). At home I kept a spare OHed AC compressor. I did surf and snipe some random peculiar parts that do go bad and could be a hassle to find. It doesn't take long to figure out what is hard to find/expensive/prone to go bad, so when deals pop up, you grab one and stick it on the shelf.
Pull your engine monitor logs and look at them every so often, although the only thing I ever caught from them were bad EGT/TIT sensors.
I did find that installing a standby alternator produced a "Karmic Neutralization Field" so that afterwards, the main alternator never, ever failed.
Ask your A&P/IA if they're good sourcing your own parts. Not common stuff they might make a margin on (which I'm completely ok with), but airframe parts that can be a PITA. They might even welcome it because some can be a hassle to find and soak up a lot of time. Be sure you coordinate to make sure they're the right parts.