People use DVCS for its features and capabilities. Because it can do more things not because it is easier to use. In the case of git the 'simple' workflow runs into some troubles because git is designed to accommodate much more complex workflows and as a result some of the core concepts have been tweaked in what people consider to be 'unintuitive' ways.

People choose vi/emacs over notepad/ed/pico for many of the same reasons and people complain about many of the same things (it's unintuitive, complicated, confusing, and so on...)