First off i would like to give you some clarification on the difference between the two.
http://www.javascriptkit.com/dhtmltutors/cssmediaqueries2.shtml
In my own experience I prefer to use width:100% as it will show at largest resolution on the web browser and each of the web browsers will show it in the best way they can. Unless the person is using Internet Explorer because lets face it the only thing that IE is good for is to install another internet browser.
So it would seem that if you where creating this specifically for mobile phones then you could use the device-width instead but if it would be opened on other devices suck as ipad or pc then width:100%; would be the preferred option.
Hope this has helped
Good luck.