It pretty much assigns them in whatever order it finds them - you can see this article (
http://kb.vmware.com/selfservice/microsites/search.do?language=en_US&cmd=displayKC&externalId=1002315) for a rundown on the process. Now if you are really dead set on changing them it can be done. You would have to:
1. go into the console (tech support mode on ESXi)
2. cd /etc/vmware
3. backup your esx.conf - eg. cp esx.conf esx.conf.bak
4. edit esx.conf and look for your vmnic entries.. will look something like
/device/000:001:00.0/vmkna
me = "vmnic0"
/device/000:001:00.1/vmkna
me = "vmnic1"
/device/000:002:00.0/vmkna
me = "vmnic2"
/device/000:002:00.1/vmkna
me = "vmnic3"
5, Order as desired by editing the string vmnicX
5. Save the edited file and reboot
You may have to readjust your nic bindings in networking when done
Good Luck