Volunteering at a clinic will not help you learn medical billing. It's a highly technical job that requires months of intense classroom/online training and testing. But you bring up the point that too little knowledge is available about what today's jobs entail in necessary training and matching with someone's aptitude and skills. She likes volunteering with Girl Scouts? She maybe should be looking at an afterschool program like after-school daycare or Boys and Girls Club, or an aide in a school or preschool instead of an office job. 

One on one career counseling and coaching is desperately needed by people like the woman in the article. Making sure their efforts are for jobs that are a good match. Unfortunately, that expertise comes at a price that the unemployed can't pay and government hasn't budgeted.