This is straightforward if you have control over the client that is sending the communications. All you need to do is set the HttpProxy on the client-side service class.
I did this, for example, to trace a web service client running on a smartphone. I set the proxy on that client-side connection to the IP/port of Fiddler, which was running on a PC on the network. The smartphone app then sent all of its outgoing communication to the web service, through Fiddler.
This worked perfectly.
If your client is a WCF client, then see this Q&A for how to set the proxy.
Even if you don't have the ability to modify the code of the client-side app, you may be able to set the proxy administratively, depending on the webservices stack your client uses.