Work profile is like a completely separate device and works independently, so any settings you apply in your personal profile will not reflect in work profile. I am still trying to get it working in work profile myself and if I succeed, I will let you know.
But they don't offer independent settings customisation for work profile for many of the items. I thought such items, Private DNS in this case, have a system-wide application.
What you are saying is likely true. That explains why I'm able to run multiple VPNs concurrently, one in the Main Profile and another in Work Profile.
I thought so too, and seems by your query here that it is not so. That a separate PrivateDNS setting is not available in work profile is also not ideal. As a workaround you could try to use local VPN based apps that allow choosing custom DNS.
RethinkDNS app comes to mind. You can add a custom dns server there (DoH).
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