Two ways of sharing directly with a friend. One is not reliable.
(a) Magnet links: Right-click a file you wish to share with your friend in your Library window, you will see Magnet link details. Copy-paste that detail onto a notecard & send your friend. They can then copy-paste that magnet link into their browser address bar & LW will open & attempt to connect to you to download that file. If they connect & are downloading, they can then Browse your files also to choose more of their choice.

(b) Direct Connect: send them your ip address. What Is My IP Address? - Lookup IP, Hide IP, Change IP, Trace IP and more... They can then open their LW, choose Direct Connect type of search & type in the ip address. If your LW is online then there's a good chance they will connect directly.

More about both of these techniques here: How to use Magnet Links & Direct Connect

* Extra points about this. It is best if BOTH of you have Chat enabled. This for some odd reason makes it easier to browse & direct connect, as well as chat of course.
When Direct Connect is used, sometimes the port needs to be specific. You can check your port via Tools -> Options -> Advanced -> Firewalls.

Personally, if I find a great host of files I am interested in, I will make a note of their ip address & attempt to Direct Connect to them at a later time. Problem with this of course is many people use dynamic ip addresses which can change, as can their port number if they are using UPnP with their modem/router to open a port for listening. The alternative method I use to find them is search a file(s) I know they have & hope (a) they are online, & (b) my search can find them.

(A search will not reach the entire network, if it did a single search would take 1-3 hours to finish. lol ... so I often use Get More Results to expand my search results, as well as browse people with similar files.)