Learn the ABC of WCF: "Address, Bindings, Contracts".
Best is to look for tutorials on the Internet as they have mentioned above, and to then create your own Service, host that service in a console app and then use VS2008/10 Add Service Reference to create the client interface to your wcf service.
WHen you get the hang of things, you must definitely invest in either Michelle's book or Juval's book, they are the best in the industry.
There are a lot of information which can really make it difficult to learn WCF but focus on the ABC and start with a specific binding and address type and work your way from there.