If I understood you correctly, you just need to make sue the workflow conditions are not there or the conditions are meeting your requirements. A workflow action is shown to the user based on these conditions.
If you mean to show every available action on the page, instead of 'workflow' dropdown, you can't do that in onDemand.
I'm not familiar with ondemand instances. However, if you want to "show all available workflow buttons for a particular issue status", the first thing I would check is the transition conditions. You can specify conditions such as "Only users with project role = X can execute this transition", so if a particular transition button isn't showing up for you, make sure the conditions are not blocking it.
Otherwise, it really depends on what outgoing transitions you have in the current status. Obviously you can't show workflow buttons for transitions that are not currently linked to the issue status.
Yes, you can have all available transitions in an issue at a given time to be shown rather than being under "Workflow". Honestly, I don't know if there's any limit but I believed that an issue shouldn't have too many possible transitions. :)
You can raise a support ticket at https://support.atlassian.com for further assistance in configuring this in your instance.
Anyway, this is the documentation for it just for your information - https://confluence.atlassian.com/display/JIRA/Configuring+Workflow#ConfiguringWorkflow-Changingthenumberoftransitionbuttons
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