First, I'd separate the benefits of going toward .NET and the ones from going toward a web application. (You may find that .NET suits your need, but web apps do not. You may also find that web apps fits your need, while .NET does not, though thats less likely).
.NET has a lot of options beyond asp.net: for example, if all your clients are Windows based, you may find that a XBAP/WPF application suits your need more... most of the power and rich client capabilities of a desktop application, with the deployement benefits, scalability and security context of a web application. Its great.
You said the beenfits of .NET were obvious, so I'll skip that.
For ASP.NET, over other alternatives, it is mainly a rich set of ressources (there's a lot of reference for web development, and getting external help, or new developers in your team is easy, third support components are very common, documentation is great, etc), it is very flexible (you can do most anything with HTML/Javascript/CSS), and it is cross platform (if someday you want to move to Macs or Unix after a big Microsoft screwup, you can change all of the clients, and you only need to worrie about the server, which is usually no big deal).
Browser based application deployement (which is not limited to asp.net: XBAP, Silverlight and ClickOnce all offer this to various degrees) has major scalability and ease of maintenance benefits, and for a user bsae of 500, its probably a large cost saving scenario. This is definately your big points if you're migrating from access.
If you have a userbase of 500, migrating to SQL Server 2005, or even better, 2008 is also a business case in itself: Snapshot locking mode alone can boost performance of your application up the wazoo, and with SQL Server 2008 you get a lot of development tool enhancement, saving money on the IT side of thing.