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First, no need to set any specific page sizes, since epub is reflow able text.
As BetterRed has said, the quality of your epub depends on the quality of your word file. As a rule: do anything with styles. Never ever format anything directly. This is even more important for headers.
If you plan to write more books, it would be worth the trouble to make a template for writing and use this for all books.
If you write fiction this should be easy. Non fiction with tables, images, diagrams etc. is very difficult. I assume you write fiction?
When you have your word document done, there are many ways to make an epub.
You could use calibre, as you did. That is okay, but you should nonetheless take a look at the stylesheet with the editor. There you could make adjustments to the formating. But all or most styles are now just named calibrex, making this a little bit tricky.
If you made a template and plan to use this for many books, a more manual way may be preferred. Either use toxxaris word addin or make it per hand. That is not that difficult. Feel free to ask for more advice, if you want to go that direction. A typical novel is not difficult to convert and you need to know just very basic css and html, most could be just copy pasted or is as easy as font-size: 1em or text-align: justify.
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