This article shows how to add default value to any system configuration option fields. System configuration option fields means those options under System -> Configuration.
Suppose, you have the following system.xml file. System.xml file is necessary to add admin configuration options.
system.xml
<?xml version="1.0" encoding="UTF-8"?>
<config>
<sections>
<mysection translate="label" module="mymodule">
<label>My Section</label>
<tab>catalog</tab>
<frontend_type>text</frontend_type>
<sort_order>110</sort_order>
<show_in_default>1</show_in_default>
<show_in_website>1</show_in_website>
<show_in_store>1</show_in_store>
<groups>
<mygroup translate="label" module="mymodule">
<label>My Group</label>
<frontend_type>text</frontend_type>
<sort_order>99</sort_order>
<show_in_default>1</show_in_default>
<show_in_website>1</show_in_website>
<show_in_store>1</show_in_store>
<fields>
<myfield translate="label comment">
<label>My Field</label>
<frontend_type>text</frontend_type>
<sort_order>1</sort_order>
<show_in_default>1</show_in_default>
<show_in_website>1</show_in_website>
<show_in_store>1</show_in_store>
</myfield>
</fields>
</mygroup>
</groups>
</mysection>
</sections>
</config>
Now, to add default value to the admin configuration options, you need to write the following in config.xml file of your module. The should be inside config node.
config.xml
<default>
<mysection>
<mygroup>
<myfield>My Default Value</myfield>
</mygroup>
</mysection>
</default>
Hope this helps. Thanks.