Thanks. There are two major things I do that make the subjects stand out.
1) The shooting phase:
I almost always use as large aperture as possible to get shallow depth of field. I also try to get close to the subjects, but leave enough distance between them and the background for that nice out-of-focus blur.
2) Post-processing.
I shoot raw and load the files in Rawtherapee afterwards. Then I manipulate the curves tool and changed the straight line to an S-shaped one, which increases contrast and saturation.
Then I check the shadows/highlights warning and if I see some areas that are too dark or too bright, I use the shadow and highlight compensation to bring them back. I like the shadows at about 4-5, anymore and they start looking unnatural to me. I guess I like dark shadows. Highlights I usually pull back a lot more, the slider usually ends up somewhere around 50-60.
The basic settings look like this:
I rarely adjust other values in the topmost part of the menu.
Then I quickly go over the other tabs, usually to desaturate the colors a bit and tweak the white balance if needed.