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No it is not possible to tell PXE what NIC's to listen/answer on.
I have found that if you change the order in which the adapter is accessed by networking services it uses the first one. I am not sure if pxeconfig uses the dns name to resolve to the server but i just made sure the interface i wanted to use as pxe was the only one registering in dns. Seems to pick that one everytime...
The only Multi Nic configuration for PXE is the Failover mode. Multi homed will not work for the Proxy