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I generally avoid having to use the vSphere CLI by doing whatever I can in PowerCLI.

If you are primarily a Unix shop then the CLI is probably your scripting environment of choice.

If you run ESXi you also don’t have the use of the Service Console to run commands so can fire up the vSphere Management Assistant (vMA) and using the CLI can run commands remotely against the ESXi host. This is especially useful for looking at performance stats with resxtop.

Here’s a good command line reference on VMware’s site updated to 4.1.
http://www.vmware.com/support/developer/vcli/vcli41/doc/reference/index.html