AWS VPC Multiple IPs

Your /etc/network/interfaces file probably has something like the following:

auto eth0
iface eth0 inet static
    address 192.0.2.10
    netmask 255.255.255.0
    gateway 192.168.2.1

This is what assigns the primary IP (it may also be DHCP). To assign a secondary IP add a post-up script to attach an additional address to eth0.

auto eth0
iface eth0 inet static
    address 192.0.2.10
    netmask 255.255.255.0
    gateway 192.168.2.1
    up ip addr add 192.168.2.20/24 dev eth0