First configure the card as you would normally. This should create a file called ifcfg-eth0 which is located in:
/etc/sysconfig/network-scripts
It would look something like the following:
DEVICE=eth0
BOOTPROTO=static
HWADDR=00:C0:4F:20:60:E9
ONBOOT=yes
TYPE=Ethernet
IPADDR=172.16.1.31
NETMASK=255.255.255.0
GATEWAY=172.16.0.1
Now to assign a second ip address, copy over ifcfg-eth0 to ifcfg-eth0:1
The contents of this file will look something like this:
DEVICE=eth0:1
BOOTPROTO=static
HWADDR=00:C0:4F:20:60:E9
ONBOOT=yes
TYPE=Ethernet
IPADDR=172.16.1.30
NETMASK=255.255.255.0
GATEWAY=172.16.0.1
Restart networking,
/etc/init.d/network restart
Now if you run
ifconfig
the output should list eth0, and eth0:1, and you should be able to ping both interfaces.