How to store data locally in .NET (C#)

I'm writing an application that takes user data and stores it locally for use later. The application will be started and stopped fairly often, and I'd like to make it save/load the data on application start/end.

It'd be fairly straightforward if I used flat files, as the data doesn't really need to be secured (it'll only be stored on this PC). The options I believe are thus:

Flat files
XML
SQL DB

Flat files require a bit more effort to maintain (no built in classes like with XML), however I haven't used XML before, and SQL seems like overkill for this relatively easy task.

Are there any other avenues worth exploring? If not, which of these is the best solution?

Edit: To add a little more data to the problem, basically the only thing I'd like to store is a Dictionary that looks like this

Dictionary<string, List<Account>>

where Account is another custom type.

Would I serialize the dict as the xmlroot, and then the Account type as attributes?

Update 2:

So it's possible to serialize a dictionary. What makes it complicated is that the value for this dict is a generic itself, which is a list of complex data structures of type Account. Each Account is fairly simple, it's just a bunch of properties.

It is my understanding that the goal here is to try and end up with this:

<Username1>
    <Account1>
        <Data1>data1</Data1>
        <Data2>data2</Data2>
    </Account1>
</Username1>
<Username2>
    <Account1>
        <Data1>data1</Data1>
        <Data2>data2</Data2>
    </Account1>
    <Account2>
        <Data1>data1</Data1>
        <Data2>data2</Data2>
    </Account2>
 </Username2>

As you can see the heirachy is

Username (string of dict) >
Account (each account in the List) >
Account data (ie class properties).

Obtaining this layout from a Dictionary<Username, List<Account>> is the tricky bit, and the essence of this question.

There are plenty of 'how to' responses here on serialisation, which is my fault since I didn't make it clearer early on, but now I'm looking for a definite solution.

Solution

I'd store the file as JSON. Since you're storing a dictionary which is just a name/value pair list then this is pretty much what json was designed for.
There a quite a few decent, free .NET json libraries - here's one but you can find a full list on the first link.