Are there any web applications out there that offer free Excel sample data utilizing fun topics like perhaps Star Wars characters?
Kaggle is a website for data science competitions. They have many datasets available for use. You generally must create a Kaggle account to get the data, but doing so is free. Many of the datasets are available as CSV files, which you could load into Excel. They're not designed for use in Excel, though, but rather for use with machine-learning libraries and programming tools (e.g., Scikit Learn), so some may be difficult to use in Excel depending on the nature of the data. There are a few Star Wars related datasets, including for instance this one that has dialogue from the movies.