Just about every time we see Sam and Dean standing or walking side by side, Dean is slightly ahead of Sam. This demonstrates two things, the first of which is that Dean will always try to protect Sam and being even just an inch ahead of him puts him closer to any oncoming danger. And the second is that Sam naturally falls into step, stands back when they’re still, and instinctively stays behind Dean when danger approaches. It’s so natural that I doubt either of them realizes they do it because I have a feeling that it started as soon as Sammy could walk.