Or to put it another way, if I define 192.168.100.0/28 as the allowed network within my 192.168.100.0/24 LAN
How will you do this??
Not with the "Local Network/s" option in the OpenVPN server settings, do you? That's just for pushing routes, it's not for securing your internal network.
It would be much nicer if I could securely specify the subnets allowed at the granularity of each client as they connect.
You can realise this with "client specific overrides" to allocate a specific tunnel address to a certain vpn client. Then you can use this tunnel address as source address in your firewall rules. It's a bit of work, but it's doable.