Hej Ulrik: Comments inline.
How do people use LibreOffice effectively?
In order for us to be able to answer that, it might be a good idea if you tell us how you work with LaTeX and HTML. For example, do you write the whole document and then begin formatting it, adding whatever codes you need to create a header, body text, bold and italics and so on, or do you add these codes as you go along?
It's been about 15 years since I used programs like LibreOffice (MS Word at the time) to write documents. Maybe a single page or two, but not anything with a structure.
Whenever I needed to write longer documents, with headings, references quotes, sections et cetera; I used LaTeX and lately HTML.
You mention 'longer' documents. Do you mean documents with chapters or at least sections? Do they have a table of contents? An index? Do they include graphics of some kind? If you are into _really_ long documents, like books, you will probably want to look at master documents. These can be thought of as a document containing other documents, rather like the include statement in a program - since you use LaTeX I assume you're a unix/linux user. A master document allows you to create your long document in passable chunks, which don't necessarily have to be a chapter, they can be bigger or smaller. You just hang them together at the end to get your book. And if your chunks are small enough you can easily rearrange them to improve the structure of your work.
Now I need to use LibreOffice, because everyone else at my job does, and it's been driving me crazy. As I was trying to insert a few excerpts into my documents, it stuck me: maybe I'm used to a completely different work-flow than what is expected by LibreOffice, and that's why nothing makes sense and things that should be easy seem impossible.
Assuming you do write your whole document in more or less continuous text without bothering about formatting until you're done with an acceptable draft, you now put on your formatting cap, and, as Tom says, there are various ways to format text. Basically they are all about marking the text you want to format, and choosing the format either by clicking an icon or entering a keyboard shortcut. In this case, by contrast with HTML (don't know about LaTeX) you get to see the effect of your change immediately, and can reverse it with two clicks.
Some of your formatting you can do more or less automatically, for example, if you want to format each chapter with a header in 14pt 3 cm down the page, and continue with double spacing, you can set up a default document with those characteristics, and just enter your text, and it will be formatted automatically for you.
Hope this helps.
//James