It is advisable to prepare a list of "pre-go live" and "post-go live" tasks based on the different areas – Basis,...
ABAP (for custom built programs and function modules) and functional modules.
Please be aware of the major changes in the areas of admin workbench and macros. Reading the release notes for SCM 4.1 and SCM 5.0 would help in knowing the major changes that you can expect and areas where functionalities can be improved with minor effort
To have a smooth upgrade, It is also essential to have a set of regression tests on critical areas in the test system after go live. The quick link /upgrade-scm in service.sap.com should give you a few guides on this.
It would also be a good idea to refer to the upgrade OSS notes (for example 588986 for Detailed Actions to perform after you upgrade to SCM 5.0) and relevant SAP forums, since they have a lot of information about upgrades.
SCM 5.1 has not been introduced yet in a big scale and is being tested. Some notes about this version can also be found but it is not mentioned available in the general SCM website.
GUI 640 is the correct version for SCM5.0.
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