Golden hour gets talked about so much that it is easy to forget it is a scheduling problem before it is a lighting one. The soft, warm light only lasts a short window around sunrise and sunset, and most of the work happens before you ever pick up the camera.
I scout the location earlier in the day, note where the sun will actually set relative to the background, and pick a spot with something for the subject to lean on, sit on or walk toward – directionless posing is the fastest way to waste good light.
Once the sun gets low, I shoot with it behind or to the side of the subject rather than in front, exposing for skin and letting the sky run a little bright. A five-minute buffer before and after the “official” golden hour is often when the color is best, so I keep shooting past the point I think I am done.