VMFS is a filesystem type, i.e. FAT32, NTFS, etc... Your vmdk's will be in volumes/luns/das that are formatted in VMFS...
There are several ways to go about setting up storage, and there are even virtual appliances such as Lefthands VAS that can make direct-attached storage iSCSI enabled and actually allow for vMotion with vm's residing on local storage.
You just need to setup your ESX hosts, configure vCenter to join them to a cluster and then configure your NAS or iSCSI on each hosts making it visible to each. From that point, you can format the storage with vmfs and start creating your VMs.
always a good reference (vmware docs ;)
http://pubs.vmware.com/vsp40u1_i/wwhelp/wwhimpl/js/html/wwhelp.htm#href=welcome/welcome.html