The skins/default/xui/en-us/fonts.xml file format is specific to the viewer (it is not a fontconfig file). You can see the code interpreting it in linden/indra/llrender/llfontregistry.cpp.
It does not accept full paths for font file names, and the names of the font files listed in it must correspond to files present in the fonts/ sub-directory of the viewer installation directory, or in your system default font directories.
Normally (i.e. with default settings), the viewer will use the fonts configured for "SansSerif", "SansSerifBold" and "Monospace" (the latter is only used by the script editor).
If it cannot find a font file for a given name/type combination, it falls back to the "default" fonts list and tries every font name in it in the listed order until it can find a font with the matching type (Italic, Bold, etc); if it still cannot find a matching font there, it uses the fallback fonts it found on your system on startup.
While rendering a character, if it cannot find that character in a loaded font, it will fall back to your system fonts (as configured via fontconfig, for Linux) and pick up one supporting that character, if any.
In fonts.xml, the "Helvetica" and "Courrier" fonts have been added as overrides for optional use in the note card and script editors (by giving their name in the corresponding debug settings: "NotecardEditorFont" and "ScriptEditorFont", with "Tiny", "Small", "Medium", "Large" or "Huge" optionally appended to their name: e.g. "CourrierTiny" for ScriptEditorFont").
This said, you raised a valid concern about Italic fonts (which are very rarely used in the UI). There is no configured SansSerif(Bold) font for the Italic type in fonts.xml, meaning the viewer uses a fallback font (which may display more or less well, depending on your system fonts).
I fixed this for next releases, by using the bundled Roboto-CondensedItalic.ttf and Roboto-BoldCondensedItalic.ttf for them. Here is the modified file you can already use with current viewer releases:
Here what Italics used to look like on my system before:
And here is what it looks like after the change: