Yep you can, you can buy yourself an access point (different to a modem/router), set this up with a different SSID to your other network, and just connect the PC's you don't want on the internet to this access point.
Or you can buy yourself a Linksys WRT54GL router, install DD-WRT on it and block any client you want through access restrictions. This is just a router mind you, you will still need to use your existing modem.
http://www.dd-wrt.com/http://www.dd-wrt.com/wiki/index.php/Access_Restrictions