You could do that, but why would you want to do this? ESXi loadbalances by default over every active network adapter, so by creating the config you stated above you will only decrease loadbalancing abilities but is you really want it, here is how:
Create a seperate port group for the vCenter server and configure explicit failover. Set one vmnic to active and the other to unused to ensure that they won't be used. That would look something like this:
For your ESXi host / other VM's: Also create or edit the existing port groups and configure explicit failover. Set both NICs as active (if you want ESXi to do load balancing over them, will also function as a backup) or set 1 as active and 1 as standby (to ensure that the second is only being used when the first one fails).
But, as I already mentioned, better would be just to configure ESXi to have 3 active adapters and let it loadbalance.