How is the default submit button on an HTML form determined?

Andrezj's answer pretty much got it nailed... but here's an easy cross-browser solution.

Take a form like this:

<form>
    <input/>
    <button type="submit" value="some non-default action"/>
    <button type="submit" value="another non-default action"/>
    <button type="submit" value="yet another non-default action"/>

    <button type="submit" value="default action"/>
</form>

and refactor to this:

<form>
    <input/>

    <button style="overflow: visible !important; height: 0 !important; width: 0 !important; margin: 0 !important; border: 0 !important; padding: 0 !important; display: block !important;" type="submit" value="default action"/>

    <button type="submit" value="some non-default action"/>
    <button type="submit" value="another non-default action"/>
    <button type="submit" value="yet another non-default action"/>
    <button type="submit" value="still another non-default action"/>

    <button type="submit" value="default action"/>
</form>

Since the W3C specification indicates multiple submit buttons are valid, but omits guidance as to how the user-agent should handle them, the browser manufacturers are left to implement as they see fit. I've found they'll either submit the first submit button in the form, or submit the next submit button after the form field that currently has focus.

Unfortunately, simply adding a style of display: none; won't work because the W3C spec indicates any hidden element should be excluded from user interactions. So hide it in plain sight instead!

Above is an example of the solution I ended up putting into production. Hitting the enter key triggers the default form submission is behavior as expected, even when other non-default values are present and precede the default submit button in the DOM. Bonus for mouse/keyboard interaction with explicit user inputs while avoiding JavaScript handlers.

Note: tabbing through the form will not display focus for any visual element yet will still cause the invisible button to be selected. To avoid this issue, simply set tabindex attributes accordingly and omit a tabindex attribute on the invisible submit button. While it may seem out of place to promote these styles to !important, they should prevent any framework or existing button styles from interfering with this fix. Also, those inline styles are definitely poor form, but we're proving concepts here... not writing production code.

HTML 4 does not make it explicit. HTML 5 specifies that the first submit button must be the default:

4.10.21.2 Implicit submission

A form element's default button is the first submit button in tree order whose form owner is that form element.

If the user agent supports letting the user submit a form implicitly (for example, on some platforms hitting the "enter" key while a text control is focused implicitly submits the form), then doing so for a form, whose default button has activation behavior and is not disabled, must cause the user agent to fire a click event at that default button.

If you want to influence which one is "first" while maintaining the visual order then there are a couple of approaches you could take.

An off-screen, unfocusable button.

.hidden-default {
    position: absolute;
    left: -9999px;
}

<form>
  <input name="text">
  <button name="submit" value="wanted" class="hidden-default" tabindex="-1"></button>
  <button name="submit" value="not wanted">Not the default</button>
  <button name="submit" value="wanted">Looks like the default</button>
</form>

Flexbox order:

.ordering {
    display: inline-flex;
}

.ordering button {
    order: 2;
}

.ordering button + button {
    order: 1;
}

<form>
  <input name="text">
  <div class="ordering">
    <button name="submit" value="wanted">First in document order</button>
    <button name="submit" value="not wanted">Second in document order</button>
  </div>
</form>

If you submit the form via JavaScript (i.e., formElement.submit() or anything equivalent), then none of the submit buttons are considered successful and none of their values are included in the submitted data. (Note that if you submit the form by using submitElement.click() then the submit that you had a reference to is considered active; this doesn't really fall under the remit of your question since here the submit button is unambiguous but I thought I'd include it for people who read the first part and wonder how to make a submit button successful via JavaScript form submission. Of course, the form's onsubmit handlers will still fire this way whereas they wouldn't via form.submit() so that's another kettle of fish...)

If the form is submitted by hitting Enter while in a non-textarea field, then it's actually down to the user agent to decide what it wants here. The specifications don't say anything about submitting a form using the Enter key while in a text entry field (if you tab to a button and activate it using space or whatever, then there's no problem as that specific submit button is unambiguously used). All it says is that a form must be submitted when a submit button is activated. It's not even a requirement that hitting Enter in e.g. a text input will submit the form.

I believe that Internet Explorer chooses the submit button that appears first in the source; I have a feeling that Firefox and Opera choose the button with the lowest tabindex, falling back to the first defined if nothing else is defined. There's also some complications regarding whether the submits have a non-default value attribute IIRC.

The point to take away is that there is no defined standard for what happens here and it's entirely at the whim of the browser - so as far as possible in whatever you're doing, try to avoid relying on any particular behaviour. If you really must know, you can probably find out the behaviour of the various browser versions, but when I investigated this a while back there were some quite convoluted conditions (which of course are subject to change with new browser versions) and I'd advise you to avoid it if possible!