Windex does not activate the adhesive on Monokote. As Rogue indicated above it is just a static bond the holds the trim. If left long enough it will eventually bond to itself, thus Monokote comes with the backing so it can be rolled. I have lost trim in flight because I didn't iron it or use trim solvent on the edges. I have a mason jar that is half full of windex and a bunch of scraps of different colored monokote, The scraps have been in the jar for 8 or 9 years and I can still take a piece out of the jar and iron to a piece of balsa. If windex activated the adhesive it would have dissolved it away.

As far as your scheme you may have trouble ironing the trim over the main color. I did a project like this and the trim would pucker where the tips of the trim color wrapped around the top of the ribs. I had to make a 1 piece panel by cutting the Monokote underneath and overlapping the trim color. It was tricky but doable.