WebServices is like a CareerLanguage. There are always enhancements, see for example http://msdn.microsoft.com/library/default.asp?url=/library/en-us/wse/html/gxaconmajorfeaturesofwebservicesenhancements.asp
Start with an overview. Try http://webservices.xml.com/lpt/a/ws/2002/02/12/webservicefaqs.html. and http://internet.about.com/library/aa_webservices_031202.htm?terms=soap+toolkit
And since WebServices started before Soap, get to know a bit of RestArchitecturalStyle and XmlRpc as well.
Next get to know a bit about related standards. Interview on standards is located at http://searchwebservices.techtarget.com/qna/0,289202,sid26_gci1000776,00.html
Learn a bit about SimpleObjectAccessProtocol (Soap), check out IwannaLearnSoap.
Now check out about Redmonds recommendation for beginners, at http://msdn.microsoft.com/webservices/understanding/webservicebasics/default.aspx
Interested in seeing how other people do it? See result and code at http://www.xmlme.com/GoogleApi.aspx
Free book online
Real World Web Services at http://www.learnxmlws.com/book/
For a handson setup, I would suggest get the Microsoft SoapToolkit going and work through a few simple samples. See http://groups.google.com/groups?th=935336380e3de7a0 for a discussion on experiences in usenet. Any better suggestions?
RubyOnRails, a popular framework, has a fairly unique approach to web services. On the one hand, the sites that Rails generates are RESTful in many ways. The entire url-to-action "routes" paradigm ensures this. At the same time, it also offers a trivially simple mapping between XML-RPC (and SOAP) and Ruby classes. This helps ensure code reuse. Since the code you use to build your XML-RPC or SOAP backend is often the same code you use to build your RESTful website.