Chris, What do you do when W does these things that make you irritated, such as undermine what you are saying to the kids, etc?
Do you stuff it all away and become resentful?
Do you wait for another time in which to address it?
I would, in the spirit of your thread title, address is as soon as possible. That is, if you are talking to the kids and she jumps in and undermines you, then as soon as you are done with the kiddos, ask her to meet you in the bedroom for a few minutes and address it. No need for a long drawn out fight, just a simple few words of "Please don't do that, just tell me later what you think I should have done and we can talk about it then." If she tries to turn it into a fight, or rehash what you just did wrong, then say "I don't want to fight about this, I just wanted to speak my piece." And then leave. I guarantee that she will be furious and stay mad at you for quite a while for the first few times you do this, but she will get over it and begin to respect you. (because really her behavior is mostly rooted in a lack of respect for you)