If I have the iMac turned off but plugged into a fully-charged, external battery (UPS) that is also unplugged, will the iMac use the coin battery....
Yes it will, and use it a lot. I killed off the internal backup battery in about year doing exactly what you describe with an older Mac. Learned my lesson.
When the computer is on wall power but turned off, a small trickle current bypasses the power supply to maintain parameters. The coin battery is to back up that bypass system should you need to unplug the computer for service or a move. If you turn everything off with the battery backup or a power strip, the coin battery kicks in.
Given that, since 2012, Apple has not sold any iMacs designed to be opened for battery replacement without a service provider, it behooves you to respect the system. Our iMacs are on battery backups with surge protection, and the backups are turned ON and plugged in all the time. That way the internal backup battery can remain doing its intended function: short-term powering to maintain parameters. Yes, we get nasty t-storms, but a quality backup power supply should be able to handle that.
The good news is that since the "New World ROM" Macs appeared in the late 1990s, a dead backup battery does not cause anywhere near the grief it did in "Old World ROM" Macs (basically those before built-in USB ports).