Basic Check Points

Hello,
I just inherited a NEW Windows 2000 Client/Server network… 3 W2k Workstations, 1 W2k Server, 1 Exchange/Outlook Mail Server, 1 Cisco 1700 Series Router, 1 Neatgear Dual Hub…

I would like to know what are the basic things I need to do (checkout) for this network, & what basic questions should I ask the Users…