Hi,
No need to worry. The reason that the LUN usage does not match the datastore usage is due to how VMFS handles blocks and reports on space. Lets start with an empty VMFS and a empty LUN. Lets say you build a new VM on there, fresh with no OS, just a 40GB VMDK file. Since you haven't really written anything to the LUN it still shows as empty while the datastore now has 40GB used. Lets say you now load an OS and fill that VM up. The Datastore and the LUN and now agreeing that 40GB has been used. Now say you deleted that VM, since VMFS is like most other file systems, it doesn't really delete the VM but rather just deletes the pointer to it. The data store will show 40GB being free but the LUN still thinks 40GB is used. No one told it the VM was delted.
So in your case it looks like at some point you moved or deleted some VMs which is why you LUN usage is higher than your datastore usage. No worry about that though, as long as you have room in your volume, all is well.
Keith