Hi
As per VMware Product Interoperability Matrixes ESX/ESXi 5.0 is compatible with vCenter 5.5, so you can add the 5.0 hosts to vCenter 5.5.
Input the existing vSphere 5.0 licenses to the vCenter 5.5.
Is the shared storage accessible by both 5.0 host and new 5.5 hosts?
If yes, then you can vMotion from 5.0 host to new 5.5 hosts as long as they have same CPU Series, the procedures are described here: vSphere 5.5 Documentation Center - Moving Virtual Machines Using vMotion During an Upgrade
Use this to check the CPU Series/Matrix: http://www.vmware.com/resources/compatibility/search.php?deviceCategory=cpu
If they are belong to different CPU Series, you can only perform Cold Migration (requires downtime) vSphere 5.5 Documentation Center - Virtual Machine Migration
Cold migration: Moves a powered-off virtual machine to a new host. Optionally, you can relocate configuration and disk files to new storage locations. Cold migration can be used to migrate virtual machines from one datacenter to another.
If you are using same shared storage, you can also do migration as below:
1. Power off the VMs in old 5.0 hosts
2. Remove the VMs from Inventory from vCenter 5.0 (take note the files location in the datastore) vSphere 5.5 Documentation Center - Remove Virtual Machines from a Host
3. Add the VMs to inventory from vCenter 5.5 vSphere 5.5 Documentation Center - Return a Virtual Machine or Template to a Host
4. Power on the VMs and check.
If the existing shared storage on 5.0 is not accessible from 5.5, you can perform LUN or Cold migration.
LUN migration requires less downtime compare to Cold migration.
LUN Migration:
1. Present the existing shared storage to the 5.5 hosts.
2. After the 5.5 can access the existing shared storage, shutdown the VMs
3. Remove the VMs from existing inventory from vCenter 5.0
4. Add the VMs to inventory from vCenter 5.5
5. Power on the VMs and check
6. Storage vMotion the VMs to new shared storage (you can also perform Storage vMotion first but you will need to present the new shared storage to the 5.0 hosts)
Cold Migration:
1. Present the existing shared storage to the 5.5 hosts.
2. After the 5.5 can access the existing shared storage, shutdown the VMs (for data consistency)
3. Clone the VMs from 5.0 hosts to the new 5.5 hosts (you can rename the old VM if you want so the new cloned VM will have the old VM's name)
4. Make sure the old VMs are powered off
5. Power on the new VMs on new 5.5 hosts and check
6. Remove the old VMs from inventory or delete it from disks
7. If you need to rename the VM's name, rename the VMs and perform Storage vMotion to different Datastore VMware KB: Renaming a virtual machine and its files in VMware ESXi and ESX
You can try to migrate 1 VM first or just create a new dummy VM and choose 1 ESXi 5.0 Host to test out the migration.