Either edge of trim is painted with body color, and is where caulking is applied at most 90 degree angles. Painting trim only, cannot feasibly include caulking, as this fails and opens up over time. Most homes need new caulking when painting the exterior, and a close inspection can determine.
You can put it around a room and probably follow immediately with the finish coat. It can be applied with brush or roller.
STENCILING. You may want designs on the walls, or perhaps even on floors and ceilings, in some of the rooms or hallway. You may buy or make your own stencils, which should be on heavy paper, stencil board, plastic, or metal. Avoid stencils made of lightweight paper which will get soaked when touched by wet paint. Your paint dealer will suggest the best paint for you to use, as it will depend a great deal on the surface over which you want to put the stenciled designs. Generally a heavy paint is used, so that it will not spread under the stencil while you are applying it.
When you plan with split complementary colors, you begin with a single reference color. Next, choose a color from either edge of the complementary color and use it. While the complementary color scheme is a little more obvious, this scheme can fail totally if you just use paler versions of your warm colors. By the same token, picking a a warm undertone for the main contrasting color and combining it with two cool tones will showcase the warm tone.
Have plenty of newspaper around. After you clean your brushes wrap them in a plastic bag.
Always use a sanding block for flat surfaces. Just your hand behind a thin piece of sand paper can leave grooves and low spots. It's also easier on your hands. For inside curves try wrapping the sand paper around a short section of garden or heater hose. This will help approximate the concave curve and help stay away from sanding through hard edges. On hard edges, like the top ridge of a fender or leading edge of a hood, you need to do this by hand. A sanding block will quickly dig right through the paint on a hard edge and take you down to bare metal. This means primer and more sanding.
You're not looking for perfection here, but you do want to eliminate every shiny spot of paint. When properly scuffed the paint should have a smooth, but dull matte finish.