Creating a Custom Payment Method For CS 2007
http://msdn.microsoft.com/en-us/library/bb219356(CS.70).aspx
Another good post about extending order system entities such as OrderForm, .. etc of CS 2007 is at:
http://blogs.msdn.com/sathishcg/archive/2006/11/08/extending-commerce-server-order-system.aspx
createing a custom payment method, explained with screenshots, by technicalmultiverse
http://msdn.microsoft.com/en-us/library/dd328095(CS.90).aspx
Also CS Guy provided a blog entry about creating a new payment method
http://commerce-server-guy.blogspot.com/2009/04/adding-new-payment-method-in-commerce.html
Although it is not detailed but helpful information about extending order sysetm for CS 2009. Steps involved in extended commerce server 2009 Systems,
by Ravi KANTH
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Create a pipeline component that processes the payment. For more information about how to perform this step, see How to Create a Payment Processor.
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Use the Pipeline Component Registration tool (PipeReg.exe) to register the pipeline component. For more information about how to perform this step, see Building Pipeline Components.
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Create a new pipeline that includes the payment processor that you created and registered in steps 1 and 2. For more information about how to perform this step, see How to Create a Custom Pipeline.
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Update the Web.config file to reference the new pipeline. For more information about how to configure a pipeline in the Web.config file, see pipelines Element.
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Follow the procedure in the topic How to Create a Payment Method to create the payment method. For the payment type property, select one of the payment types that start with the word “Custom”.
Beware when adding a new payment type, order of class definitions and tables in OrderObjectMappings.xml have to be the same, otherwise it does not work.
http://social.msdn.microsoft.com/Forums/en-US/commserver2009/thread/cac83579-4fc9-44fd-97c0-13cb1ec7fbad
Do not externalize your web.config sections, you may face issues with order system api.
http://social.msdn.microsoft.com/Forums/en/commserver2009/thread/77aefb7a-5547-4489-a3c9-6292f48e7221