Regarding the documentation and getting up to speed, the unit tests are always the best place to start. There shouldn't be anything in NHibernate that isn't unit tested (if possible), and the tests should work. These are great examples of how the code should work and how it should be used.
The official memcached site is
http://www.danga.com/memcached/, and the .NET client is at
http://sourceforge.net/projects/memcacheddotnet/. Documentation is very scarce, but fortunately memcached is pretty easy to use.
I'd say the memcache 2nd-level cache is less than alpha - let's call it 'experimental' for now. In other words, try it, see if it works, and let us know.