Document everything you can.
Backup configs, make sure you save them frequently when things are working.
Get a good network management/monitoring package which uses SNMP to monitor the equipment.
Take as many classes and training sessions as you can.
Purchase vendor support for equipment. Cisco TAC is invaluable when the excrement hits the oscillating device. When the network is down, and the boss comes into the server room to ask when it's back up, it's much more comforting to hear that the vendor is helping you investigate the issue than to hear you have no idea what the problem is or when it might be fixed.
Build a lab to test/learn new protocols/ways of doing things. Have a couple servers in there, as well as the same type or smaller versions within the same family. If you're running Cisco 3945 routers in production, a lab with 1720s running 10 year old code doesn't help you troubleshoot production issues or test code upgrades.
A good podcast which covers CCNA/CCNP level topics with examples:
http://www.ciscohandsontraining.com/
How to backup your devices:
http://www.shrubbery.net/rancid/
Netdisco, good tool for network discovery and host tracking
http://www.netdisco.org/
Join and read network mailing lists. NANOG, Cisco-NSP, Juniper-NSP are a good place to start.
http://puck.nether.net/mailman/listinfo/ to subscribe to several of those.
Beyond that, good luck. Speaking as someone who has been doing systems/network administration for close to 15 years, you will learn something new every day. If you don't, you're not trying hard enough.