On my R6, "TotalShoot" matches the total of captures I made with my camera since I bought it, whether using MS or ES, but "TotalShutter" seems to match the mechanical shutter actuations, because its value increments by one everytime I turn my camera on, and everytime I take a picture using MS, but it does not change when I take a picture using ES, so I guess we can pretty much subtract "TotalShutter" from "TotalShoot" to get the amount of electronic actuations.
Also, video recording doesn't change the value of "TotalShoot"