I called Verizon today and changed from unlimited data to PAYG with a data block. After this was done, I changed my connection settings in the advanced tab and selected "My work network" in both the drop-down menus. I also changed the #777 broadband access number to a dummy number.

What other changes are needed to the phone once you block data so that any/all applications will use wi-fi whenever it is available?

Under wi-fi settings -> network adapters, the "my network card connects to" is currently set to "Work". Should that be changed to "The internet" to allow all applications to be able to access data via wi-fi?

Are there any other tests, besides using IE, that can be done to ensure data is indeed blocked but everything else is working via the wi-fi connection?