Speedplay suggest their pedals are easier to unclip at 3 or 9 o'clock. I tend to unclip them at 6 o'clock anyway.
When to unclip? Gee, when you know you are going to stop and just before you stop.
Unfortunately, I've got a habit of only unclipping the left foot. I don't know if I would/could react fast enough to unclip my right foot if I had to in an emergency. I don't think so.
..rickko..