Do you only need to apply once a day, or do they wear off as the day progresses?

Maybe, and yes.
The thing is different pheromones have different rates at which they dissipate from the skin. There are some estimations of pheromone-in-alcohol-spray half life by MarkL:

sorry, it is mainly focused on the ones men wear, but you get the idea. Ishine doesn’t last that long and may require periodical top-ups if the situation needs it. -none, which you probably won’t be wearing, lasts for ages; I don’t know about copulins and their half-life. You may develop a feeling for when hits are wearing off and self effects and all that, and might reapply. Or, you might have made such a good impression initially with the pheros that you can get on without reapplying; just let the momentum of the day’s events carry you along…