I do have an attorney friend that I would totally trust, but his family is struggling financially. I've helped them out in the past so I think it would be kinda awkward.
We don't have an accountant but we do have a tax guy that I also trust. I was going to start doing my own taxes (hate spending the money for him to do it and my calculations marched his for 2012), but last year my husband was out on a long medical leave of absences and there were some tax issues.
We have given through a church if the individual attends our church or if we knew what church they went to. Because of my work schedule, we haven't been able to attend very often lately and had to find one with an evening service. Since our attending is sporadic, we're not really involved. One of the reasons we've gone to helping people versus organizations.
Not trying to shut down ideas--just thinking through them. Too bad Vanguard doesn't have a option outside of IRS approved charities. I think I'll email our advisor.
If you're giving to an IRS-approved 501(c)3 charity then the charitable gift funds will keep you anonymous. Fidelity has a good fund, so does Vanguard, and I think Schwab also has one.
I use DonorsChoose.org to give to school teachers, although your anonymity is only guaranteed by using a different name & mailing address.
Giving anonymously to deserving individuals is tough. If this was a Dickens novel then you'd hire a lawyer on retainer to give your cash to people while retaining your anonymity through client confidentiality. I like Forbes' idea of using your accountant's name on an LLC, although that requires an accountant to really trust you. Another option could be giving through a church, or asking a local community fund if they'd be willing to do it for you.