Whisk vinegar, sugar, salt and water in a small bowl until sugar and salt dissolve. Place onion in a jar; pour vinegar mixture over. Let sit at room temperature for at least 1 hour.
Hollandaise modified slightly from The Food Network Test Kitchen, quick-pickled red onions from Oliver Strand via Bon Appetit, June 2012.
It may be tempting to spiralize the potatoes ahead of time and then bake right before using, but I'd recommend against this, since the potatoes will oxidize and stick together. I'd recommend pickling the onions and steaming the cauliflower the night before, then finishing everything else close to serving time if you're trying to divide the work and time.
Your choice if you want to keep or remove the cauliflower leaves (I removed them off of the cauliflower pictured in this post).