Might it be possible to create a VSS-simulation build on an ESXi server in a home lab and, if so, what might be the limitations?
At the moment, it’s not possible. Maybe Cisco supports it in Virl someday…
If you have access to Cisco’s PEC, they have a couple of labs for the 6500s that you can use to practice VSS. If you have access, the labs are free.