BTW - Apple support claims I can get two externals working by daisy chaining off Thunderbolt 4 (I don't believe that though and didn't want to go through expense / returns to try without trying this forum first). Thanks again.
That statement is (mostly) true, but misleading.
Your iMac does not have Thunderbolt 4 ports. One of the requirements for Thunderbolt 4 certification is the ability to drive two monitors over USB-C (DisplayPort) or Thunderbolt. Your Mac has Thunderbolt 3 ports. Thunderbolt 3 equipped computers are allowed to support multiple monitors (some Intel Macs do), but it is not a requirement.
If your Mac had a Thunderbolt 3 or Thunderbolt 4 port, and was capable of driving multiple external monitors, then the only way to drive two monitors off a single Mac host port would be to connect them through Thunderbolt. E.g., Mac to Thunderbolt dock, and then plug both monitors into that dock. A Thunderbolt connection provides a wider data "highway" than a plain USB-C (DisplayPort) connection would.
Even then, you would not necessarily be "daisy chaining off Thunderbolt 4". A much more likely setup would be for you to have two non-Thunderbolt displays or adapters plugged into the Thunderbolt dock. The Thunderbolt dock would be distributing two video signals between two displays, but neither display would be "daisy-chained" off the other, or would even be aware that Thunderbolt was involved.