@TinFoil:
I don't really need wireless clients to talk to one another, just out to internet. Would it be a big pain if I did?
No. If you use the default 'lan to any' as a template for the rules on the other interfaces all the clients will be able to talk to each other. The default rule on LAN is very open, you can replace it with something much more restrictive or add block rules if you don't want that. However because the clients will be in different subnets they won't 'see' each other, in Windows Network Neighbourhood for example, even though the traffic is allowed.
@TinFoil:
Go into OPT1 for example, name it LAN2 set it to static IP but use 192.168.25.1 / 24 . Go into DHCP server, make sure it is also going to serve up LAN2 (will make pfSense be the one handing out DHCP leases, even direct to the wireless clients). Finally go into firewall rules setup an allow all for outbound but set it as LAN2 subnet?
Looks good. The firewall rules in pfSense work to restrict only inbound traffic, with respect to the interface, so if you allow traffic with destination 'any' on LAN it will be able to reach the LAN2 subnet even if you haven't added rules on LAN2 to allow it.
@TinFoil:
Finally, can I make the newly created subnets also access the WebUI? If so, how.
The webgui listens on all interfaces so it will be accessible from any interface that has firewall rules to allow it, which the default rule does.
Put up a sceenshot of your rules if you're still having any trouble.
Steve