There are many ways to go about adding colour to a greyscale pic.
One method is to add a new layer over the greyscale image and change the layer's blending mode to something like colour, multiply, or overlay (play with them to see the difference). Then just start painting with colour. Alternitively, you can set the brush to use a blending mode and paint directly onto your greyscale layer (removing the safety net of using a layer). Some people also begin by using a hue/saturation adjustment with the colourise option checked, which directly colours the grey.
I normally start by adding a layer, changing the blend mode, then flood filling it with a base colour. After that I start to block in colours and gradually build up from there using different layers and blending modes. If the colours start to get away from what I'm wanting I use a curves adjustment to get them back on track.