Just an update, I raised this issue with Asus, however it looks like they acknowledge that their Guest networks actually have no segregation.
In this case Guest Network SSID by name, but not actually as a Guest Network by function, which is why the whole network is accessible.
If anyone is looking to replicate this issue, it can be done with the following:
Primary router running a GUEST network (any slot or frequency), with access intranet disabled.
Repeater Setup:
Start with a wiped Asus router (factory default).
Connect to the ASUS_5G network, or directly to the router via Ethernet cable.
Go to 192.168.1.1 in a browser.
Click Advanced Settings.
Choose Operation Mode> Repeater mode.
Pick the GUEST network from the list and key in the GUEST password.
Pick Automatic IP.
Set 2.4GHz and 5GHz Repeater networks (e.g. STUDIO and STUDIO_5G).
Set router login name and password.
Wait for router to reboot.
Test: Connect PC to Primary Router SSID (or via Ethernet to primary router) and a second device to the STUDIO_5G SSID. The device on the STUDIO_5G network is able to discover and access the PC on the primary network - this is the issue.