Continue for adding multiple tablerate
Now edit app\code\core\Mage\Shipping\etc\system.xml
What you do is add one more tablerate XML after the first <tablerate>
<config>
<sections>
<shipping translate="label" module="shipping">
<label>Shipping Settings</label>.
.
.
.
<carriers translate="label" module="shipping">
<label>Shipping Methods</label>.
.
.
</freeshipping>
<tablerate translate="label">
.
.
.
</tablerate>
<tablerate2 translate="label">
.
.
.
> </fields>
</tablerate2>
<tablerate3 translate="label">
<label>Small Packet Shipping Mehthod</label>
<frontend_type>text</frontend_type>
<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>
<fields>
<handling_type translate="label">
<label>Calculate Handling Fee</label>
<frontend_type>select</frontend_type>
<source_model> shipping/source_handlingType </source_model>
<sort_order>7</sort_order>
<show_in_default>1</show_in_default>
<show_in_website>1</show_in_website>
<show_in_store>0</show_in_store>
</handling_type>
<handling_fee translate="label">
<label>Handling Fee</label>
<frontend_type>text</frontend_type>
<sort_order>8</sort_order>
<show_in_default>1</show_in_default>
<show_in_website>1</show_in_website>
<show_in_store>0</show_in_store>
</handling_fee>
<active translate="label">
<label>Enabled</label>
<frontend_type>select</frontend_type>
<source_model> adminhtml/system_config_source_yesno </source_model>
<sort_order>1</sort_order>
<show_in_default>1</show_in_default>
<show_in_website>1</show_in_website>
<show_in_store>0</show_in_store>
</active>
<condition_name translate="label">
<label>Condition</label>
<frontend_type>select</frontend_type>
<source_model> adminhtml/system_config_source_shipping_tablerate3 </source_model>
<sort_order>4</sort_order>
<show_in_default>1</show_in_default>
<show_in_website>1</show_in_website>
<show_in_store>0</show_in_store>
</condition_name>
<export translate="label">
<label>Export</label>
<frontend_type>export</frontend_type>
<sort_order>5</sort_order>
<show_in_default>0</show_in_default>
<show_in_website>1</show_in_website>
<show_in_store>0</show_in_store>
</export>
<import translate="label">
<label>Import</label>
<frontend_type>import</frontend_type>
<backend_model> adminhtml/system_config_backend_shipping_tablerate3 </backend_model>
<sort_order>6</sort_order>
<show_in_default>0</show_in_default>
<show_in_website>1</show_in_website>
<show_in_store>0</show_in_store>
</import>
<name translate="label">
<label>Method name</label>
<frontend_type>text</frontend_type>
<sort_order>3</sort_order>
<show_in_default>1</show_in_default>
<show_in_website>1</show_in_website>
<show_in_store>1</show_in_store>
</name>
<sort_order translate="label">
<label>Sort order</label>
<frontend_type>text</frontend_type>
<sort_order>100</sort_order>
<show_in_default>1</show_in_default>
<show_in_website>1</show_in_website>
<show_in_store>0</show_in_store>
</sort_order>
<title translate="label">
<label>Title</label>
<frontend_type>text</frontend_type>
<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>
</title>
<sallowspecific translate="label">
<label>Ship to applicable countries</label>
<frontend_type>select</frontend_type>
<sort_order>90</sort_order>
<frontend_class>shipping-applicable-country</frontend_class>
<source_model> adminhtml/system_config_source_shipping_allspecificcountries </source_model>
<show_in_default>1</show_in_default>
<show_in_website>1</show_in_website>
<show_in_store>0</show_in_store>
</sallowspecific>
<specificcountry translate="label">
<label>Ship to Specific countries</label>
<frontend_type>multiselect</frontend_type>
<sort_order>91</sort_order>
<source_model>adminhtml/system_config_source_country</source_model>
<show_in_default>1</show_in_default>
<show_in_website>1</show_in_website>
<show_in_store>0</show_in_store>
</specificcountry>
<showmethod translate="label">
<label>Show method if not applicable</label>
<frontend_type>select</frontend_type>
<sort_order>92</sort_order>
<source_model>adminhtml/system_config_source_yesno</source_model>
<show_in_default>1</show_in_default>
<show_in_website>1</show_in_website>
<show_in_store>0</show_in_store>
</showmethod>
<specificerrmsg translate="label">
<label>Displayed Error Message</label>
<frontend_type>textarea</frontend_type>
<sort_order>80</sort_order>
<show_in_default>1</show_in_default>
<show_in_website>1</show_in_website>
<show_in_store>1</show_in_store>
</specificerrmsg>
</fields>
</tablerate3>
</groups>
</carriers>
</sections>
</config>