I'd say Post Processing
Post processing certainly gives you more flexibility.
The main point is that by taking a colour picture and subsequently using a channel mixer (Photoshop) you can choose the relative amounts of red, green and blue that go into your final BW image.
For instance you can elect to use only the red channel for converting to BW and throw away green and blue (as for the reasons for doing so, I expect you will find them in the tutorials you wrote about.)
Note that this will not result in a black-and-red picture: the channel mixer first controls colour channels to your will, then goes BW.
If you take the picture with your camera set in BW mode, the only way to get these effects is by putting a coloured filter in front of your lens, but then again: you put on the filter, take the picture, see the result, and if you don't like it maybe you can try another colour. In postproduction you have three sliders and a preview checkbox set. And you can even change your mind: you re-open the original file and do things all over again.
Hope this helps.