Beginners question: Will this setup work?

With IPFire 2 you can’t do exactly the same thing since you have only 2 users/clients nets GREEN + BLUE. For every VLAN you need (I’m not sure that you really need them) a seperate NIC and configure them in the “NIC assignment” via the web ui as VLAN. Also your switch needs to be configured for static VLANs. In my opinion this is not usefull, since you will need at least 6 NICs for the GREEN (+BLUE) network and wired connections to the switch.