If you are painting both the wall and woodwork I suggest you paint the wall first, and then paint the woodwork. In my opinion, it is much harder to touch up paint on woodwork and keep the finish looking good versus touching up the wall. Use a glossy paint to give your finish a shine and help make dirt and fingerprint cleanup easy.
Make sure there is no lose materials on the trim. Painting the surface won't hide imperfections like chips, cracks or peeling paint. Using a stiff putty knife, scrape off any lose paint. Check for nails that are sticking out and hammer them in using a nailset. This will sink the head below the trim surface. Using wood putty, fill in any small cracks or nail holes. Use wood filler for larger areas applying it with a flexible putty knife. This will help hide imperfections in the wood.
Once the wood putty has dried it's time to sand the trim. Use Extra Fine (280-320) sand paper sand the trim with the grain to gain a smooth finish. This will also smooth out any areas where the wood putty is not flush with the trim. After you have done this wipe down the trim with a damp washcloth to remove any dust created from sanding and give it time to dry.
Now it's time to tape off the wall or glass that your trim is attached to. Be sure to use painter's tape that has low adhesion, otherwise you may end up damaging the wall or door that you tried to protect. Regular masking tape can also be difficult to remove from glass if left on too long.
You can expect to pay $10 to $20 for a good paint brush, but it will be well worth your money. If you use a cheap brush you will have a difficult time keeping the finish smooth and glossy. Apply a good layer of paint on the trim by dipping the paint brush often and applying it to the trim. Repeat this technique using a good amount of paint, but not too much that it starts to drip. Once you have completed applying a good coat of paint, take the brush and start at the top or side of the wood work and in one smooth motion run the brush from one end to the other. Keep the brush at a 45 degree angle and apply light pressure. You will want to do this before the paint starts to dry.
This isn't a job you should rush. If you want a high quality finish you need to invest the proper amount of time and supplies into the job. Using good brushes, paint and wood fillers is critical. You're saving money by doing it yourself; don't redo the job because you saved money on supplies.
Sources:
http://www.minwax.com/products/wood_maintenance_and_repair/
http://www.rd.com/how-to-paint-woodwork-tips-and-techniques/article17684.html
Published by Matt Hobbs
I received a BA in Music from Bethel University. I have remodeled 3 different houses doing a variety of work on them like siding, windows, kitchen/bath remodels and unfortunately much more. I currently work... View profile
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