OK to update, here is where I'm at (all the cabling is set up), and I believe the problem I was trying to avoid is happening:
Workstation Mac Pro:
- Ethernet to Router: DHCP static IP bound to Ethernet MAC
- WiFi to Router: DHCP static IP bound to WiFi MAC
- Thunderbolt to Mac Mini: Manual IP 10.0.0.1
- Logged into my iCloud account
Legacy Mac Mini
- Ethernet to Router: DHCP static IP bound to Ethernet MAC
- WiFi to Router: DHCP static IP bound to WiFi MAC
- Thunderbolt to Mac Pro: Manual IP 10.0.0.2
- Logged into my iCloud account (for reasons of iCloud Drive)
The workstation has filesharing enabled, and only a single drive is shared.
On the Mac Mini, I can see the workstation in the Finder sidebar, and if I click on it, it will automount the entire workstation's filesystem, using the workstation's local credentials it's getting from iCloud.
I don't know how to tell what network interface that's using.
More importantly, I don't want it getting filesharing credentials via iCloud - I have a bad feeling the only solution to this is to remove the Mini from my iCloud account.
I can disconnect the auto connection, and manually set up an SMB connection to 10.0.0.1, and it will show only the single drive as available, but again, I personally don't know if that means I can be sure it's actually transiting the connection via the thunderbolt link.
I would also like to bind Apple Remote Desktop to the thunderbolt link, as the Mini only has gigabit ethernet and TB should provide for a more responsive experience, but whenever I try to configure connecting to 10.0.0.2, while ARD shows it as 10.0.0.2, if I get the attributes of it, it's showing its address as a 192.x - again, I don't personally know enough to know if I can attribute that to meaning the link is happening over the TB cable (I did my OS X Server Admin qualification with Apple ~19 years ago, so I'm very rusty from my sysadmin days).
So this seems to be where I'm at, and I imagine the next step is to waste several hours of my life trying to get Apple support to let me speak to someone senior enough that they know what a "Mac Pro" is (true story), and then see whether I can speak to someone who knows how to do the networking thing.
*edit* and FWIW signing the Mac Mini out of iCloud solved the login issue - now it only shows the login option for the dedicated filesharing user I created, and only mounts the specific drive I shared.