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Working software can still miss the workflow
A team can return to spreadsheets even when the new application is technically functional. If routine work takes more effort in the system, people find ways around it.
Observe the actual work
Talk with the people performing the task, including those handling exceptions. Map handoffs and data entry before deciding which screens to build. A manager's overview and a field worker's daily needs may be quite different.
Build adoption into delivery
Validate prototypes with users and introduce changes in manageable stages. Training, clear responsibilities, and feedback after launch are part of implementing a system, not separate extras.