It looks like you have it set up correctly, but you created your own Smart List. Try modifying the "Possible Duplicates" system list to filter on "Full Name" and the "Member of List".
So I actually did something similar to what Amy L suggested, I set up a smart list with the filters "Full Name Is : (Here I copied and pasted the full name column of the excel spreadsheet I had) and "Email Address is Not Empty" and "Email Invalid: False." This seemed to work very well, it yielded around 140 names we already had email addresses for in the system (of a 450 name list). This little work around will save me a lot of time. Thanks to both of you for your help!
See a screen shot of the solution below.