WCF is really the "new" standard and new generation of web service - and even more generally, communications - protocols and libraries for the .NET world.
Whenever you feel the need to have two systems talk to one another - think WCF. Whether that'll be behind the corporate firewall in your company LAN, whether it's across the internet, by means of a direct call or a delayed message queueing system - WCF is your answer. Mehmet has written a really nice summary of how WCF is the unification of a great many communication standards that existed in the Microsoft world before WCF.
I would think with the "Learning WCF" book, you should be a lot better off than with Programming WCF - that's quite advanced stuff already!
One of the mainstays of WCF is the architecture that you always talk to your service through a proxy - whether that service runs on the same machine using NetNamedPipe binding or halfway around the world in Down Under on a server - no difference, you always go through a proxy. That then also allows WCF to be so extensible - thanks to the proxy always being between the client (your application) and the service, it offers excellent ways of extending the behavior and the inner workings of WCF to your liking and needs.
WCF basically builds on SOAP communications - so interfacing and using existing SOAP services should be no problem at all. With the WCF REST Starter Kit and in the upcoming .NET 4.0 release cycle, WCF will also extend its reach into the REST style web communications, if that's ever going to be a requirement of yours.
All this really shows one of the biggest strenghts of WCF: it's a unified and extremely flexible and extensible communication framework, that can handle just about anything you throw at it. That alone is more than enough reason to learn WCF (which can be dauting at first, I agree!), and you won't regret the effort you put into this endeavor.
Marc