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Doing it from the Nook varies by device, but easiest way is to log in to the website and open your library (here). On any book that has the "Lend Me" tag you can lend it once, to one person. Just click on the blue "Lend Me" banner. You'll be prompted for the email address of the person. That's all there is.
If you want to experiment, since you can only do it once per book, try downloading a free book with Lend Me enabled (like Anne of Green Gables) and lend it to a friend who also has a B&N account and Nook.
I found it on the website after fumbling around for a while. On my nook it would just open the book. I love my nook and it is easy to do once you find the answer. Why make it so hard to find?