I'm under the assumption that you simply put optionName = "optionValue" as noted in the Upgrading to Juicebox Pro section of the Wordpress Plugin page on the Juicebox website.
Yes. For example, you could enter options such as the following into a gallery's Pro Options text area:
backButtonPosition="TOP"
backButtonUseIcon="TRUE"
backButtonUrl="http://www.example.com/index.html"Please note that WP-Juicebox strips out any Lite Options which are entered into the Pro Options text area to avoid duplicate entries in the gallery's XML file. Lite Options can be set in the gallery settings window via the individual controls.
Also, curious as the best practice for changing themes/messing around with the look of the wordpress plugin.
You can certainly change your WordPress theme and this will change the look and feel of your WordPress pages. However, no matter what theme you choose, your Juicebox galleries should remain constant (and can be modified in the gallery settings window).
If you want to see how a gallery looks when using certain configuration options, then try using JuiceboxBuilder-Pro on your computer. It supports all Pro Options via individual controls and has a live preview window which shows you how your gallery looks as you make changes. If you want to replicate a particular layout, then you can save the gallery (on JuiceboxBuilder-Pro's 'Publish' tab), open the gallery's XML file in a plain text editor, copy the configuration options and paste them into a WP-Juicebox gallery's Pro Options text area.