100' roll still might not transfer enough heat when the water is flowing a lot, like during a shower. As for durability, the PEX might not last all that well inside the boiler, especially if the thing ever over heats or you get a hot spot inside the water jacket that the PEX would run through. I think that if you want to try it out, it wouldn't be too hard to fix if it didn't work out for you. All you simply would need to do is cut a hole on a flat face for a plate that the coil could run in and out of and seal that plate up with a gasket between the boiler and the plate. If the PEX coil doesn't heat enough water or fails, you'd simply shut down your boiler and drain off enough water to reach the level of that plate, then pull the plate and the PEX coil out through the hole. If you did a standardized hole, you could then insert a pre-made copper coil in and bolt it up for a very quick fix. You could also make your own domestic coil with copper tubing too (if the PEX coil failed). I say give it a whirl but leave yourself a way to easily remove it if there is a problem. 100' coil of PEX is cheap enough.
BTW, I love GARN's. If I didn't already have a boiler I'd look long and hard at getting one and setting it up in a Garn Barn.