IPv6 - there's gonna be a demand for people that know it
Get a home network going with old computers. Set up DNS, DHCP, WiFi, WEP, WPA2, Radius, multicasting on Linux and Windows in IPv4 and IPv6. Learn about cat5, cat6, crossover cables, TDR, single-mode fibre, BGP, IGMP, TCP,IP,UDP,ICMP etc.
Sometimes it's easiest to learn by doing, and with free software and cheap hardware it's not that expensive.
But you probably need a diploma, too, to satisfy the paper pushers. The practical experience helps at interview and, of course, to actually do the job.
Network security - learn TCP/IP, play with Wireshark, NMAP, Netstumbler, learn about filesystems, operating systems, scripting, HTML, SMTP, email, firewalls, iptables. Go to DEFCON in Vegas.