It is.
For the first one, you'd have to push a route to the client for that particular website. You can even push it by dns name, but you have to set manually in the installed OpenVPN client's config the allow-pull-fqdn parameter.
For the second one, it works out of the box.
You'd create two OpenVPN server instances (running on two different ports) for the two types of users. Assign the created server's tun interfaces as pfSense network interfaces, and then you can apply firewall rules to them as usual (for the first one to only allow access through wan, and for the second one allow acess through the second nic lan).
You'd have to set up hybrid NAT too, for the first one to access that special site from behind the VPN tunnel.