I think Jayne is probably the best example of how I would play a CN character in D&D.
However, while I firmly believe CN is maligned, it seems to always be the go-to alignment for people that tend to be more disruptive than the average player.
On another note, someone mentioned demons earlier - I think they actually provide a great example of how Chaotic is NOT random, but instead describes the dichotomy between collectivism and individualism.
The Abyss is ruled by demon lords with literally armies of demonic followers. Each individual demon is a scheming, back-stabbing embodiment of CE, and yet they still are able to form armies, follow orders, etc. - when it suits them. If they think a different course of action is more likely to provide a bigger benefit (or lesser consequence) to themselves, they have no problem disobeying whatever orders they may have had.
The key here is that they are not acting randomly - if one had access to all the same information and insight into their situation that the demon did, one might be able to imagine a scenario from their point of view, weigh the options and figure out what that demon might decide to do, assuming one also understood the demon-in-question's individual motivations.