Yes, that's really interesting. From what I know, Louboutins generally are known for not being comfortable. With the Hot Chicks it's the combination of the height and tight/stiff toe box. The Pigalle are way more comfortable, but I've worn them so much that you could almost call them "worn out". Though they still hold up well, I'm sure I can wear them for many years to come.
If I would wear the Hot Chicks as much as the Pigalle I think they'd get more comfortable too with time.
Maybe I'll try my walk around the block in my boots this week. I'm a bit concerned that it will be very uncomfortable, but I got to start at some point.
My indoor wearing also results in a lot of sitting, but as you say it still gets you familiar.