Well, after you fire out the Debug Process screen, to your dismay, you found more than one W3WP.EXE with different Process ID. The question is, which W3WP.EXE to be the debugger attached to ?

You can find it using command line utility called IISApp :

The AppPoolId refers to the Application Pool where your web application resides. Usually it resides in DefaultAppPool. To verify that your application is indeed resides in certain Application Pool, you can use IIS Manager 6.0 snap in :

In the above example, the gear below the "DefaultAppPool" is all of the web application that resides in that particular Application Pool.
After determining which application pool that your web application resides, you can write down the PID shown by IISApp, and perform the right choose, and hence, your debugger will break to your desired location.
Whereas about precisely how you do the debugging, you can consult another posting in this blog. Wish you a happy web service debugging :) !