Magento allows you to define 5 email addresses in backoffice, to add some, create (or use an existing) system.xml in a new (or existing) module like this
<config>
<sections>
<trans_email>
<groups>
<ident_relance translate="label">
<label>Relances</label>
<frontend_type>text</frontend_type>
<sort_order>10</sort_order>
<show_in_default>1</show_in_default>
<show_in_website>1</show_in_website>
<show_in_store>1</show_in_store>
<fields>
<email translate="label">
<label>Sender Email</label>
<frontend_type>text</frontend_type>
<backend_model>adminhtml/system_config_backend_email_address</backend_model>
<validate>validate-email</validate>
<sort_order>2</sort_order>
<show_in_default>1</show_in_default>
<show_in_website>1</show_in_website>
<show_in_store>1</show_in_store>
</email>
<name translate="label">
<label>Sender Name</label>
<frontend_type>text</frontend_type>
<backend_model>adminhtml/system_config_backend_email_sender</backend_model>
<validate>validate-emailSender</validate>
<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>
</name>
</fields>
</ident_relance>
</groups>
</trans_email>
</sections>
</config>
In this case, this will create 2 entries in the core_config_data table : trans_email/ident_relance/email and trans_email/ident_relance/name.
To retrieve values, use this :
Mage::getStoreConfig('trans_email/ident_relance/email');
Mage::getStoreConfig('trans_email/ident_relance/name');