>I don't think my ISP can easily intercept the content of DoT DNS requests.
No. But they can intercept connections to the IP addresses returned by such DNS queries.
>They would need a valid certificate for 1.1.1.1#cloudflare-dns.com or 9.9.9.9#dns.quad9.net from a trusted (by me) CA, correct?
In order to MiTM such requests, yes.
>Now obviously that's not impossible but is a VPN any better in that scenario?
You're only considering the DNS queries. Once you've received a response to your DoT/DoH query, presumably you'll want to connect to the returned IP address, right?
Your ISP can absolutely capture those packets, and even if the payload is encrypted, the headers are not -- so while they might not be able to access the data, they have full access to the metadata. Unless you use a VPN, which will encapsulate the headers as well.
All that said, my issue is with DoH/DoT, since devices can stealthily bypass my DNS controls (including ad/telemetry blockers like Pi-Hole) and unless I block all TLS/HTTPS traffic (making my internet link mostly useless), I can't stop surreptitious connectivity.
I'm not as concerned with my ISP as I am with not being able to block ads/tracking/telemetry. Apologies if I wasn't clear about that.