Normally, when I'm painting digitally, I use the oil technique of starting from a mid tone, and then working the lights and darks from that.
If I were to try and give a watercolour feel, I'd start with white and work light to dark, because that's how watercolours work.
I'd also suggest doing a fair bit of the painting with light washes, and having the brush set to "multiply", to emulate the transparent and additive effect that watercolours have.
Perhaps it might be an idea to make a palette of some standard colours, with variations of them fading to white, to give you something similar in feel to diluting the paints with water.