There is more than one way to do this depends on requirements, e.g. time frame, amount of data, downtime. Prior to migration, you need to get your new setup working and have all network mapped out matching to old ones for your VMs to work.
Migration between vcenters (de-register from one and register in another) is certainly the quickest and easiest however it requires both vcenters have access to the same storage. But if you are prepared to move old hardware to new datacenter, then this is not a problem.
You can also join the old hosts WITH old storage to new vcenter, you then can just cold-migrate or vmotion all VMs to new hosts. And if you planning to continue to use old hosts, you can just upgrade them to 5.5
Once dust settled, you can move on to upgrade vmtools and hardware as suggested in upgrade guide.
If non above is possible, you then have to bring over those VMs over WAN or removable media using some backup/replication or converter application.