I'm not exactly sure what you are trying to do but if you go to your IPv4 properties you can use the alternate configuration to add different Ip's, DNS servers and so on.
You can also use the advanced tab to enter the TCP/IP info for more than one connection.
System Manufacturer/Model Number Home built OS Windows 7 Ult, Windows 8 Pro, CPU Q9650-4.275GHz, E8600 4.5GHz, E6750-3.8GHz Motherboard Evga 780i FTW Memory G.Skill PC2 9600 1200Mhz 5 5 5 15 2T Graphics Card GTX480 Sound Card Asus Xonar D2 Monitor(s) Displays HannsG Screen Resolution 1680X1050
Keyboard Logitech G15 Mouse Logitech G9 PSU ThermalTake Toughpower 1000Watt modular Case ThermalTake XaserV Cooling Xigmatek S1283 Hard Drives GSkill Phoenix Pro 120GB SSD Internet Speed T1
choose specific network connection for interent access problems?