Is there a local group who recycles/reuses electronics? (maybe turning old PC's into Linux boxen, to be given to low-income families) Donate a couple items and drop off $20.
There are very small, not well known women's/family shelters that are always desperate for anything from socks, underwear, blankets, toys, to dishes, cleaning supplies, etc. Sometimes not easy to find these - they tend to keep a low profile, but their services are vital for people who find themselves in a very difficult situation.
Check the websites of local charities - they usually list the specific things they are most in need of.
I donate stuff to Goodwill... after I have offered it to groups like the ones listed above, but they don't have an immediate need.