I'm not sure I follow the first part of your question.
Let's say I have records with data on cities in California and Nevada.
I specify the following sort order:
My records will sort first by state, then by city alphabetically. That produces two groups of records--An alphabetized list of California cities followed by an alphabetized list of Nevada cities. Does that answer your question?
As to exporting,
The current sort order of your found set is what will be exported so you would find the records you want to export, sort them into the desired order, then do the export.
If you export the records as an excel file you can have the field names be exported in the first row. Now you can copy and paste this data into MS Word to get your data with the header row of field names like you wanted as a table in Word.
Let me explain further. In the layout I created, each record has a field for the quote and a field for the author/date/page # (and a couple of others for tracking purposes). The layout also includes three coding fields, each with 5-15 values to choose from in coding a record. Every record is assigned a value from Coding Field 1 and a value from either Coding Field 2 OR 3. For example, a record might be coded for (1) "Psychology" and (2) "Development" or (1) "Rites of Passage and (3) "Models."
I was asking how to sort the records (currently done by the three coding fields) so it sorts like this: Coding field 1 value and Coding field 2 values and then Coding field 3 values. For example, all the records with a (1) Psychology and (2) Attachment; (1) Psychology and Behavior; etc. and then (1) Rites of Passage (the only field 1 choice that uses field 3) and (3) Liminality; (1) Rites of Passage and (3) Model; etc.
My second request was how to set it up so that when I export the sorted records, it lists the header and subheader for each group of records (see example above). Exporting to Excel prints out the field name but not the value (and only does it once for the whole list).
Does that help?
For the first part of your question, you can use the "custom order based on value list option."
For the rest, there are ways to use a group by option in your export, but that won't repeat the column heads with each group. Maybe another poster can chime in on that one.