Enabling, disabling, or modifying the EVC mode does not effect any powered on VMs.
A given EVC mode can however only be set if the physical hardware (CPU) supports it, and if no powered on VM has CPU features in use which are not supported for the given EVC mode.
Since CPU features are exposed to VMs only at power on, you can migrate VMs between ESXi hosts with the same, or newer CPUs (given it supports the exposed features) even without EVC being enabled.
That said, there's an issue with Skylake CPUs for which Intel introduced a new CPU feature, that they dropped again in later CPU models (see e.g. https://kb.vmware.com/s/article/76155 for details). Depending on the ESXi version/build on which a VM has been powered on, and the VM's virtual hardware version, you may need to shut down that VM in order to migrate it to the new EVC enabled cluster.
André