First of all I don't recomment to add in web.config your settings. If you want to upgrade your Sitecore than you have to merge manually your web.config.
If you still want to add setttings in web.config you need to have something like :
<configuration>
.....
<appSettings>
<add key="YourSeetings" value="your value" />
...
</appSettings>
.....
</configuration>
From C# code you need to use
ConfigurationManager.AppSettings["YourSeetings"]
If you have your settings on section /configuration/sitecore/settings
you need to use from C# code :
Sitecore.Configuration.Settings.GetSetting("yoursettingsname");
Your config file will looks like :
<configuration xmlns:patch="http://www.sitecore.net/xmlconfig/" xmlns:set="http://www.sitecore.net/xmlconfig/set/">
<sitecore>
<!-- General settings -->
<settings>
<setting name="YourSettingsFieldName" value="{1EPR25B2-98C6-45BF-B9E4-824ECAAEF499}" />
</settings>
</sitecore>
</configuration>