Well there are plenty of guides out there on the internet that will teach you about networking, And you do got something to learn to wire your house up and learn about ethernet cables and cable speeds, cat-5, cat-6... 10/100/1000 mbit stuff.... But on the software side .... for LMCE it is recommended you let the system do the assigning of ips, subnet masks, QoS, etc automatically.
So aside from setting up the internet connection part of your LMCE set up (ip address,subnetmask, gatway), and even this part is mostly plug-and-play with most ISP's (via DHCP), there isn't much to tinker with without breaking something. It's great to know/learn this stuff, but its not recommended you experiment with learning this stuff on your LMCE box.
In most situations, configuring the networking portion of LMCE is as simple as..... placing 2 Network cards in your Core/Hybrid, connecting 1 cable to ethernet card 1 to your DSL/Cable modem, the other cable to ethernet card 2 -> a network switch/hub, then placing any other networking devices such as computers from their network card -> switch hub. And thats surprisingly it, in most scenarios.
Try also looking in the user setup's section of the wiki, some people have drawn diagrams of their setup which may include the networking portion of how they connected their devices. Also take a look at http://wiki.linuxmce.org/index.php/Wiring_Considerations
for network cabling suggestions.