Layer style, stroke has faceted edges

Stroking a path is more complex than ones first intuition would be.  Your 200 PX stroke clearly shows for its not as smooth as you thought it would.   If you look at a normal 200 wide px stroke about a path. You will see the outside edge Path and the inside edge pate are different shapes and different then the stroked path. Your Stroke is not a normal 200PX stroke. Its more like half of a 400PX stroke. One edge of your strike is the stroke path shape.  A normal stroke shape more or less the shape of a selection the has been expanded and contracted.  The stroke center path is the path stroked. Abrupt changes in path direction effect the inner and outer path.  Photoshop has shape stroke options to deal the these abrupt changes. Along with three stroke option Centered Normal, Inner and outer.  Layer styles Stroke has the three stroke options inner, outer and centered but nor the smoothing options. So a Layer Style path can be quite different then the same Shape stroke path. You could remove your layer style Duplicate your shape layer then  edit the top shape set ts fill to none and stroke to 200 px orange  align inner and corners to rounded.  It will be a better inner stroke than the layer style stroke.

Based on what I see, the lighter orange shape is not very smooth. I know you said that you created it with the pen tool, but was anti-aliased turned off when you made the path from the pen tool into a selection? Something is eroding that edge and so the stroke that you are then applying is just showing it.