Performance & Fault Mgt starting point- pls point me in the right direction

Hey all, I’m a sergeant in the AF tasked with setting up a ‘network services’ shop at my base; the tools I have at my disposal are HP Openview, MRTG and CiscoWorks LMS-
for these, what would be be a good starting point for what I should be monitoring to keep the pulse of our network and/or see problems before a breakdown occurs? And if you would like to add ‘suggested’ monitoring levels/threshholds for them, that would help me out even more. Thanks.