You can start from here:
Introduction to Workflow 4.0
http://channel9.msdn.com/learn/courses/VS2010/WCFWF/IntroToWF/
To learn more about WF4, read the WF4 document:
http://msdn.microsoft.com/en-us/library/dd489441(v=VS.100).aspx
To learn how to apply WF4 in real applications, check samples:
http://msdn.microsoft.com/en-us/library/dd483375(v=VS.100).aspx
To get deep into WF4, follow this blog(go with flow):
http://blogs.msdn.com/flow/default.aspx
and this one (matt's blog)
http://blogs.msdn.com/mwinkle/default.aspx
And .NET endpoint:
http://blogs.msdn.com/endpoint/default.aspx:
If you can read Chinese, I recommend you read through this blog:
http://www.cnblogs.com/foundation/
If you get any problems, Ask your question in WF4 forum:
http://social.msdn.microsoft.com/Forums/en-US/wfprerelease/threads