I adjust first if it is necessary. Some nutes precipitate (fallout) if you don't adjust pH prior to adding the nutes if your water has high pH. If you are using rain water, you don't have to adjust first. If you are using tap, I'd adjust the night before and check the next day just before adding nutes. Peppers do best with lower pH than 7. Most people aim for 5.8-6.2 or so. Keep in mind that a single point of change really means 10 times. So one full point is really a significant difference.
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