You need to ask questions that let them show off their full understanding of a system. People without organization skills will focus on one area and not explain the whole.
My favorite is to have someone explain to me what happens when a browser makes a HTTP request to a web URL, which has . Network guys will tell you all about the request and response, web developers will focus on the front end, devOps will tell you how all the pieces communicate, etc. My expectation is for someone to at least be able to give a high level of all those things, while also having detailed knowledge of some specific areas... and seeing how they choose to answer such an open-ended question tells you quite a bit about where their focus and attention lies.