I had a couple of extraneous thoughts.
-You're mixing the entire system down and that's the main source of heat. So, you don't have higher temp source for, say, the kick heater. Even though there's a separate zone for the dhw tank, the low temp gets involved there too. Low temp distribution is working out except for those two instances, and the excellent mini split is taking care of the off. There probably isn't a separate zone for the kick heater anyway, and it'd be a big deal routing pipe with a pump out there just to get a higher temp mix.
-With the DHW, however, since all the stuff is in the boiler room, can you isolate that from the main mixing valve so that it gets higher temp water from the main storage tank? Also, I'd put in an anti scald (mixing) valve around the dhw tank just in case, plus you can charge that up as high as you want with no worries.
-Now, how about this: my original oil boiler system never had any boiler circ pump-I think that's generally the case. It sounds like you have an additional feed pump from the main storage tank in front of the zone pumps? Is that really necessary? Everything is pretty close.