Inspect your cayenne pepper seeds and discard any damaged or discolored specimens. Additionally, remove any seeds that are smaller than the rest of the group. Cayenne plants are stronger when they start from strong seeds.
Place the seeds in a cup of water and allow them to sit for 12 to 24 hours. This serves two purposes: The seeds' outer shells are softened so they have an easier time germinating, and the cayenne seeds that are more likely to sprout sink to the bottom of the cup. Scoop out the floating seeds and place the remaining seeds on top of a plate to dry.
Poke holes in the sides and bottom of a plastic cup and fill it with seed-starting mix. The holes allow for water drainage and adequate air circulation for the roots.
Drop a few seeds on the top of the mix and cover it with another light layer. Water your container so that the soil is moist, but not waterlogged. Keep this water level going at all times.
Wrap plastic cling wrap over the top of the cup and poke holes for air circulation. Place the cup on top of a warm area, such as a computer monitor, to provide the heat cayenne peppers need to germinate. A temperature range of 75 to 85 degrees Fahrenheit is ideal.
Look for green, upside-down "u" shapes on top of the soil. Cayennes generally take five to 11 days to germinate, but this is dependent on the specific variety you are growing.