sending a magnet link to your friend or a list of your files is one way. Control-click (right-click) files in the Library to bring up those options.
The 4.1 betas have also added connecting directly to the IP:port of another LW user from the search box (see
http://www.limewire.com/english/cont..._history.shtml for the 4.1.1 release notes).
Since the code is open source, LimeWire's code could be used to create a private network but requires more skill and knowledge. Any file placed in your shared folder right now though, is publicly available.
LAN transfers are fast--they show up in the search panes as "ethernet" results and are marked in blue.
cheers