I think you're mixing the terms up a bit and that's adding consufion :smileywink:
Storage is added to the ESXi hosts directly. vCenter has nothing to do with the storage, only the hosts.
a Cluster is an object that you configure in vCenter. You add hosts to this cluster. ( There's also an object "datastore cluster", but that's another story :smileywink: )
Your general steps would be:
1. Install one ESXi host (or both, doesn't matter)
2. Connect to the host with vSphere client and add iSCSI storage
3. deploy vCenter Appliance on the host.
4. Configure appliance
5. connect to the appliance with vSphere client / webclient ( I would go with the webclient https://appliancename:9443/vsphere-client as the old vSphere client will run out in the next vSphere version )
6. create a cluster
7. add the already installed host to the vCenter and move it into the cluster
8. install second ESXi and also add it to vCenter and move it into the cluster
Tim