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I migrated an outside window trim trick inside my old house...

Go to the hardware store and buy a nice piece of thin, somewhat flexible sheet metal. Trim the piece down to a manageable rectangle (18x10 works for me). Then use the piece as both a straight edge/guide and brush blocker as you proceed to paint the last inch along the trim. If you follow in one direction and don't oversaturate the brush, you will see a brilliantly straight line being formed. Another trick is to use a smaller, straight brush. For some reason, angled brushes tend to make a more jagged line. As you proceed section by section, wipe any excess paint onto a rag and flip the sheet metal piece if any buildup occurs. Keep it clean and the same piece will be a great tool forever.

Good luck!
~Mark