Reading these two articles should give you the information you need to add your own custom configuration variable, which will automatically give you a UI to enter values in the Admin.
If you want to set a default value for your new configuration variables, there's a top level config.xml
node named default
which will let you do that. Consider the following
<config>
<!-- ... -->
<default>
<web>
<default>
<cms_home_page>home</cms_home_page>
<cms_no_route>no-route</cms_no_route>
<cms_no_cookies>enable-cookies</cms_no_cookies>
<front>cms</front>
<no_route>cms/index/noRoute</no_route>
<show_cms_breadcrumbs>1</show_cms_breadcrumbs>
</default>
</web>
<cms>
<wysiwyg>
<enabled>enabled</enabled>
</wysiwyg>
</cms>
</default>
<!-- ... -->
</config>
This structure in config.xml
sets default values for the following config variables
web/default/cms_home_page
web/default/cms_no_route
web/default/cms_no_cookies
web/default/front
web/default/no_route
web/default/show_cms_breadcrumbs
cms/wysiwyg/enabled