There is indeed a homeless shelter/drop-in centre in town which has "job-readiness" sessions for homeless men - and they do look for new, high-quality clothes for interviews - so unless ex's hoard includes thousand dollar suits from Italian designers with liberal return policies (never say never ...) I may just take everything wearable over to the shelter.
I know from Al-Anon that I need to be focusing on my own recovery and not obsessing over the alcoholic and why they do/did what they do/did - so I'll report that my own reaction to the news about ex's office hoard has been a couple of nights of disturbed sleep with dreams about ex (something I hadn't been troubled with before), which led to waking up in the middle of the night and having to remind myself "no, he's dead, so [bad thing in dream] isn't real and won't happen". This in turns suggests to me that forging ahead getting rid of ex's crap (literal, financial and psychological) as rapidly as possible is the right thing to do.