Not a silly question at all! The peak time to test is 2-4pm. My tests always worked anytime between 10am-6pm. I've even tested later than that. It's just best not to use FMU. LH metabolizes later in the day, so your results with FMU may not be accurate. Whenever you test, you want to hold your urine for as long as you can. At least 3 hours is usually okay, without drinking much during the wait.
I always peed at 3pm and then stopped drinking anything. And I would test when I got home from work at 6pm. I never missed my surge doing it that way. However, some women have a short surge and test mid-morning and afternoon.
Here's a site that you might find helpful:
POAS ~ OPK FAQ