Easiest way to develop such an application (this is a high level answer of "how do develop an app when you can't see the classified or protected data" not "how do i make a web portal with an excel backend") is to get "dummy" data.
You make the dummy data just as protected, but give the developers the ability to see the data on the other side of the wall. You make sure the datatypes are the same (the only thing different should be values) and go from there. That's the easy way. After the app is developed with the dummy data, it's deployed and people with access to the data "connect the pipes" and away you go.
As to using an excel sheet as a backend to a website..please look into MySQL or MSSQL or some other database solution. The developer coming after you will thank you.
If you can't because of management..ripping open an excel file directly is not for the faint of heart, but microsoft does provide an api to access the insides. I've done it once..and don't remember how to off the top of my head, but perhaps someone more skilled remembers the api. The easier road is to have that workbook output to CSV (which is easily parsed).