I would recommend learning at least some VMware since VMware will be what is hosting your OS.
The VMware admin probably doesn’t need to learn much about Exchange since he will simply be hosting the OS that the Exchange servers will be running on. Make sure that he’s aware of any potential storage issues, and that he knows to correctly align the virtual disks when presenting them to the OS.
You should learn VMware at the foundation layer so you can understand how it works and then definitely read best practice to Exchange hosting within Vmware since their are various methods that may or may not work in your environment. You will need to understand your SAN infrastructure as well since your system may be affected by performance if not designed correctly. Depending on the size of your Exchange environment, you may want to review to see if you can have dedicated paths to the SAN (fibre or iSCSI).
Setup a little meeting with your VMware guy and Storage guy, and then discuss the best methods that are available to you from their viewpoint. Using this meeting, you can review the various documents to fit your environment. Exchange virtualized not just improves your bottom dollar as per costs, it provides you a DR/BCP capabilites hard to simulate with physical hardware.