If you're new to painting, I would HIGHLY recommend visiting All Things Thrifty and read her post Painting Furniture Hmmm. Love the black top with the black accents and white. It would tie in the black bed frame.
How To Paint Furniture: I used a waterbased acrylic alkyd enamel. It's water based so it cleans up easily with water, but the enamel formula gives it a harder finish like an oil based paint. - Love Home Decor