The secret to knowing your camera settings better than you can imagine is easier than you think. This technique will not be new to you if you have studied any kind of time management courses. In those courses, they recommend you take advantage of the times when you are waiting. The most common example is the times at the doctor's office - the recommendation is to have a book to read or bring study material.
I am not suggesting that you bring your camera to the doctor's office, but there are other times that you can find to do the same with your camera in your hand. When I first started with my DLSR the most difficult thing for me was finding things on the many menus on the camera. Not only was it difficult to find what I wanted, but I also did not know what most of them were used for.
So I have my camera in my hand at times when I am waiting or idle in some fashion. I will share two times that work the best for me and I am sure you can find similar time slots. The times to find are when you are not taking photos so you can experiment with the settings.
The first time I use is when I am watching TV and am forced to endure the crass commercials. It is during the commercials, that I pick up my camera and start perusing menus. This also works well because I have access to my computer to look things up on bing.com.
The second opportunity comes during my travel. If you fly, ride a bus, travel by train, or other modes of travel that you have time make use of that time to study your camera's menus.