Have a look at the posting by Brian Graf over at Adding License Keys to vCenter with PowerCLI | Brian Graf's Virtualization Blog
I've cut out the code below which works in our lab environment in PowerCLI 6...
# Assumes you're already connected to the vCenter server where the license should be added
$LicKey="xxxxx-xxxxx-xxxxx-xxxxx-xxxxx"
$VcLicMgr=$DefaultVIServer
$LicMgr=Get-View$VcLicMgr
$AddLic=Get-View$LicMgr.Content.LicenseManager
$AddLic.AddLicense($LicKey,$null)