Painting appliances is definitely possible. It's important that you use a finish made to stand up to temperature extremes and daily wear and tear (i.e., banging around of pots, pans and people). Epoxy-based finish paint is a good choice for painting appliances. With its long drying time and application challenges, you'll get the best results if you let an experienced pro handle the job.
There are also some attractive specialty paints for appliances available on the market, such as Liquid Stainless Steel, a water-based automotive-grade finish that lends the look of brushed stainless steel to refrigerators, dishwashers, ranges, cabinets and more.