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When I used to starch my military uniforms the procedure was to lay the garment flay on the ironing board, spray across one side of the leg ( crease to the side ), and press ( iron ) then flip and do the other side for a crisp seam that stayed that way all day long, same thing for the shirts. flat areas stay crisper and flatter when sprayed and ironed all at once, do the shirt front in two halves, back, in fourths starting at the collar, and sleeves separately, be careful about the temp of the iron because starch will help them get shiny ( glazed ) fast, keep the iron at medium or low temps.
One thing i remember about starch is that buttons under fabric will leave a nasty mark if you iron over them, so pocket flaps and such need to be done so that it is not over the buttons, undo it, flip it open, and iron the flap by itself. ( not sure if this applies to anything but military uniforms )
Do not starch your boxers.
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