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In order to do this you would most likely have to use an Ethernet shield. I am not sure if the Ethernet shield works with Galileo. I have a couple, but have not tried them. I don't know if anyone has tried using an Ethernet shield.
If you want to use a Ethernet PCIe card, you would have to buy an mPCIe to PCIe expander and an Ethernet card. In theory it is possible, but do not know of anyone who has done that.
What I would recommend is using Ethernet and Wi-Fi. You can buy a Wi-Fi mPCIe card (and all the accessories needed) for the Galileo cheaper than an Ethernet shield.
The next part is getting them to work. From Linux, it should be no problem. I am pretty sure the Linux OS could handle multiple networks. However, from Arduino, I am not sure the Arduino libraries support two network devices at the same time?
The Ethernet on the Galileo does not use any of the Arduino pins. This is very nice since you do not have to worry about pin conflicts with other shields.
The Galileo is pin compatible with an Arduino Uno, So, in theory, if you have an ethernet shield for Arduino, it should, in theory work with Galileo.
As Alexander pointed out, it looks like the Arduino Ethernet library is using the built in Ethernet port. You would have to find a different library in order to get an Ethernet shield to work. I am sure there are plenty of Ethernet Arduino libraries out there that work with shields, but I if they have the same name "Ethernet" I think that might cause a conflict in the IDE? So, you might have to change the name?
Not sure if that is useful in your case, but just in case: with Linux it is very easy to configure any number of different IPv4 addresses/subnets on a single Ethernet interface. Nothing specific to Galileo.
See for instance this article: http://www.linuxplanet.com/linuxplanet/tutorials/6553/1
(For IPv6 multiple addresses per link is even the default)