Choose the right tool for the job. You will either need a 2.5 inch angled sash brush, or painting edger, or you may wish to try both. The paintbrush you purchase should be of the highest quality, for even distribution and application of paint. If you purchase a painting edger, you will want the kind with an adjustable handle for easy angling.
Tape the baseboards along the edge where the baseboards meet the wall. This step may be optional but is recommended. Keep in mind that sloppy applications of paint can still lead to some paint leaking beneath the surface of the tape, so putting the tape on the baseboards should not become an excuse to paint in a way that is quick and messy.
Spread tarps out over the floor and tape them to the painter's tape along the baseboard, so the baseboards are completely protected. It is recommended that you cover the entire floor with tarps during the painting process, although it is not a requirement for protecting the baseboards.
Dip your paintbrush or edger in the paint and gently remove excess paint by scraping off the excess along the edge of the paint can or paint tray.
Place the paintbrush or paint edger along the edge of the wall where the wall meets the baseboard, angled away from the baseboards.
Run the paintbrush or edger along the wall making a solid line where the wall meets the baseboards. Do this slowly and patiently. Refresh your brush with paint as needed. When this is finished, you may paint the rest of the wall with a roller and your other painting tools.