Picked up this tip on a discussion board a few years ago, tried it and love the results- no matter how silly it seems.
1) Get naked.
2) Put hat on head.
3) Get in shower.
4) Lather it up with shampoo.
5) Rinse thoroughly.
6) Let hat air-dry.
Having the hat on your head lets you scrub with your hands kind of hard without bending it out of shape. After you do the outside all over, take it off and scrub inside and around the headband, then rinse while off.
You'll be amazed at how much brown grungy gunk is in the water as you rinse it off. Hat should be completely dry after sitting overnight.
I've had some pretty disgusting looking hats (not ones used for umpiring, but for yard work, working on the car, etc.) come out looking great from using this method. Umpire hats, which I take generally good care of anyhow, come out looking almost like new.
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