That's a great question. I'm a trained/licensed firefighter/EMT/HAZMAT responder, so hopefully I can help with this.
I find it EXTREMELY advantageous to have a fully staffed station(s) for response, along with an auxiliary of responders if there is the need for them. To be the most efficient, firefighters would also be EMT's/Paramedics/Nurses. Since 99% of modern emergency response is for medical purposes and not firefighting, having all firefighters medically trained would make the most sense for response.
As far as response goes, I've thought about this for a while, too. Perhaps instead of having a separate firehouse, it could be incorporated into the hospital/medical facility. One big problem I think there is today is that everything is separate. Having a hospital with not only an Emergency Department, but with extended medical stay, surgery, specialized treatment, etc. Then incorporate First responders of every type: EMS, Fire, Police (in whichever way it is deemed needed). This way, EMS and fire personnel can be utilized in the Medical facility until an emergency arises outside of the facility, and the staff which is designated ONLY for the facility can stay and continue to work with patients.
In regards to the actual fire fighting effort, having an initial response with fully staffed trucks would be paramount for the entire city, with a supplementary "volunteer" response either to the scene, or to an annex which has more apparatus and gear so there can be a more efficient fire attack. The primary reason for line of duty deaths for firefighters is not from the fire itself, but because of stress related injuries. Therefor, it would be essential to have an auxiliary response to make sure that the fire does not spread and that our initial responders are working in the safest manner possible.
Hope this helps with some ideas, and I'm sure I'll have a more in-depth plan at a later time.