Get-esxcli is a good option.
However it is also possible to use directly the API via PowerCLI.
To associate a new VMkernel interface to the default VMotion stack
The HostNetworkSystem has a method AddVirtualNic
This AddVirtualNic needs a HostVirtualNicSpec as a parameter.
The HostVirtualNicSpec has a property netStackInstanceKey
You can use there "vmotion" instead of "defaultTcpipStack"
It should also be possible to modify or add a new network stack.
The HostNetworkSystem has a method UpdateNetworkConfig
It needs as a parameter HostNetworkConfig
This object has a property netStackSpec of type HostNetworkConfigNetStackSpec
And in it netStackInstance of type HostNetStackInstance
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