Can we deploy using both a Web service, Web form, and Win form architecture simultaneously (these are the products we are “centering”)?

Yes you can.
Visual Guard allows you to secure as many application as you want in the same repository, whatever the technology: .Net (Win form, Web form, web service, Silverlight, WCF, WPF) or other technologies as long as they are capable of HTTP requests (C++, Java, Php, Delphi, Ruby...)
(This would require to use the VG Server).