not necessarily ... it probably just thinks that it can use the first as it's primary interface ...
if you had netmasks set up, so that each ip was on a different subnet then it would probably work ...
i have 3 cards in my machine and i can ping -i <any interface> and get the host i want, but then again it's because of the routing. it uses the primary ip to route to the destination machine ... i guess you could look at the ifconfig -a ...
Jon