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If your customer needs to port the data into their own systems then yeah you have a candidate for a web service. Especially if the 2 systems (yours and theirs) are disparate.
Assume for a moment that your customer has a Client Application that reports on the data your webform collects; and that today you provide this data to your customer with a spreadsheet or a copy of the access database which your customer manually loads into their data systems.
In this scenario a web service makes sense for you and your customer allowing your customer to now subscribe to the data and stuff it into their own data systems to be extracted by their Custom Client Application.
If your customer is not technical you'll probably have to build the web service (hosted on your side) and the subscribing application (hosted on their side). The subscriber would call the web service and persist the results into their data systems. You could also integrate the subscriber right into the Client Application.
TheNige is right, it's totally up to you as to what you want to expose.
Check out XML for ASP.NET Developers [Paperback] by Dan Wahlin. It's a pretty fast read that will get you up to speed quickly. I picked up a used copy for $8.