For anyone reading this in future, here's what we've been told by the team on Feedback Assistant - I simplified the example to using ping to ping another client on the network, which doesn't work as of iOS 18.0.
Please know you can’t use IPv4 to communicate between client devices, you have to use IPv6. IPv6 link-local is perfect for this.
You can use ping6 with any of the configured IPv6 addresses to verify.
I can now confirm that using one of the configured IPv6 addresses, we can communicate between clients on the iPhone Hotspot. It's an unfortunate change for us, but one I expect we'll need to handle - our products don't currently support IPv6.
Topic:
App & System Services
SubTopic:
Networking