I unclip my left foot first, which perhaps is odd because I'm right-handed? The right foot always gets clipped in first, unless I'm having an off-day and neither foot wants to clip in right away.
I wish I could do a trackstand. Maybe one of these days, I'll get adventurous and first try it out on my mountain bike which has platforms -- once I find a soft patch of grass, of course.
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...what's your goal?