Remove all items from inside and around the fireplace. Clean up any old ash, and remove it; the ash could get stirred up by the activity in the area and mar your freshly painted surface.
Apply painter's tape to the areas adjacent to the plaster fireplace surround. Covering these surfaces with tape will protect them from paint and help you get a clean finish.
Lay a drop cloth on the floor in front of the fireplace to protect the hearth from paint drips and spills. Part of the drop cloth should be inside the fireplace to catch any drips there, as well.
Use a foam brush to apply primer around the edges of the surround, then fill in the center with a small roller. Work quickly, and clean up any drips right away. Let the primer dry for at least an hour, then apply a second coat. Let the primer dry overnight.
Shake up the paint or stir it with a wooden paint stick, then pour it into the paint pan.
Apply paint to the edges of the fireplace surround with the foam brush, then fill in the large, flat areas with the mini roller. Let the first coat dry completely.
Examine the fireplace surround for dripped paint or flaws, and use a piece of sandpaper to fix these areas. Add a second coat of paint using the same method you used for the first coat. Let the fireplace dry overnight.
If desired, add a latex or water-based sealer coat to the fireplace surround. This step is optional, but sealer can protect your fireplace and make the surround easier to clean.
Remove the painter's tape and discard it, then remove the dropcloths and trash them.
Allow the fireplace to dry for several days before using it.