I'm a purger but I'm married to a hoarder (in terms of stuff). Conversely he purges the money and I hoard it LOL
Seriously, my DH has tons of odds and ends. So many that he can't find them when he needs them and often ends up re-buying stuff he already has. There is no order to his chaos and he complains about a lack of space in a 3000 square foot home plus a 25 x 25 garage (the entirety of which is filled with his crap) My car accumulates snow and ice in the winter while his junk stays nice and dry.
He has to be forced to purge and organize. It really requires a lot of handholding. But it has gotten much easier over time.
As for advice, I would enlist the help of an organized friend. Sometimes you need an impartial set of eyes. If both you and DW are hoarders , you'll talk each other into keeping everything and there will be no change. When you've determined what you don't need, start posting on craiglist, freecycle. Give it a set date, if it doesn't sell/go by xyz, donate it and get a tax deduction or take it to the dump.
I really think organizing is a lot like any other goal. It's a series of small steps. If you want to take it to an extreme (as I do periodically) check out www.flylady.com
I find the system as a whole to be overwhelming but it has a few great points 1. You didn't get disorganized in one day, you won't be able to fix it in one day, and 2. Take 15 minutes every day, NO MORE, and declutter in a given zone, switch zones weekly.