I need to repost my complaint about UPS (and others) refusing to cater to the residential workers market, and I will, but for now lets just summarize it for you. A lot of people work during the day and it’s not useful or even green to drive all over town attempting to deliver things to people who are not home so delivery services need to add a class of delivery that comes from 6-9 or so. This way you can be home when your package arrives.
With that said, my idea is simple and it can start very small. Open a company (or even start a collective) where you all share an address and you have someone at that address all day to accept deliveries. Then, from 6-9 you re-deliver any packages received that day (or even save money and do deliveries every 2 days). Maybe even offer an email/IM/phone call on receipt and allow people to pick up on their way home.. whatever. The concept is to build a very high quality service layer on top of fedex/ups/usps, etc. especially for people who work at home.
How much extra would you pay to have this service?