Hello,
  First make sure that the only excel add-in is the one for your current version of Quality Center (as multiple versions of the add-in will cause compatibility issues, you can check through the control panel and uninstall programs section to find installed add-ins).  NExt you need to make sure that the you have registered the client after installing the add-in.  The CLient registration can de completed through the add-ins page (or it can be accomplished through the following from the url box in the browser:  http:///qcbin/start_a.htm?common=True ).  If these do not solve your issues you can run the HP Quality Center Connectivity add-in from the add-ins page (I would recommend re-running the registration after that as well).
Hope this helps.