My husband is fairly tidy anyway, and he has a study where he can have his bits and bobs, so it doesn't bother me. My children are only 3 and 5, but the older one amazed me by copying my example and sorting out her room! I went through their toys with them, and they were very clear on what they did and didn't want!
With regard to actually getting rid of stuff, I try to put things straight in the car, so it forces me to take it somewhere. Most clothes went to charity clothes bins, but I sold some of the more decent stuff on eBay. I'd never used eBay before, but was surprised how easy it was! (and addictive, I found myself scouting the house for what to sell next!). But it's only worth bothering with eBay if something has a decent value, otherwise not worth it I think.
Toys we took either to a charity shop, or our local hospital, where they were much appreciated.
Quite a bit of my 'stuff' (komono) went in the bin, but I recycled what I could. I don't like waste, but some things really weren't any good to anyone.