Your question is too poorly defined to give a complete answer, but here's the skeleton of one.
The missing part (the meat if you will), is a function that takes any two coordinates and tells you which one is 'greater' than the other. Without a solid definition for this, you won't be able to make anything work.
The rest, the skeleton, is pretty simple. Sort your list of vectors using your comparison function. For five vectors, a simple bubble sort will be all you need, although if the number of vertices increases considerably you may want to look into a faster sorting algorithm (ie. Quicksort).
If your chosen language / libraries provide sorting for you, you've already got your skeleton.
EDIT
After re-reading your question, it also occurred to me that since these n vertices define a polygon, you can probably make the assumption that all of them lie on the same plane (if they don't, then good luck rendering that).
So, if you can map the vector coordinates to 2d positions on that plane, you can reduce your problem to ordering them clockwise or counterclockwise in a two dimensional space.