"How/when do most of you use Polartec Powerdry (of the Cap 2/4 or MEC T2 variety)? As a base layer next to skin or as a midlayer? How do you layer with it?"
I usually wear the heavier stuff as a mid-layer. With the Cap4/R1 versions, it really comes down to the cut, IMHO. For example, an R1 Flash pullover has a slim cut and is designed as a heavy base layer, where an R1 jacket has a much fuller cut and should be considered a mid layer. I haven't had a chance to compare the Cap 4 versions.
Any of the versions would be comfortable against the skin and could be worn as a base layer if your usual base was wet or being laundered.
If they fit you could layer them up anyway that you like, BUT, as much as I like fleece, there is a loosing return for too many fleece layers as a deliberate layering system for a hike with a wide range of conditions. If you are expecting colder weather, a puffy takes over. Then the question is, do I take base/mid and puffy? One combo I've come up with is to boost the thickness of my base layer so I'm comfortable hiking with a load, adding a wind/rain shell as needed and also adding a fleece vest to cover some of the colder weather while under way. That would look like a Cap3 long sleeve 1/4 zip top supplemented an R1 vest and wind/rain shell and the puffy for rest/camp.