For me, English has been a mostly literary language for years with most spoken forms coming to me with simultaneous subtiles. So, it's rare that I encounter a new spoken word that I haven't read before, but with time and familiarity you develop some kind of heuristics I guess (and enough of English comes from French that there is no need to be too lucky).
I now live in Japan and used to guide, in English, foreign tourists in Kyoto. Amusingly only native speakers seemed to sometimes have difficulties to understand my strange pronunciation/accent.
That's where the problem comes in: You can't pronounce those words without context. "A row of people was watching the row". "A tear in the painting brought a tear to my eye", "I bow to your skills with the bow".
The concepts are interrelated. If, for example, a given language uses a single representation for two sounds, it is perceived only as accent.
The difference between sh and zh in South American pronunciation of 'yo' (Argentina and Uruguay) is perceived as accent for a Spanish speaker. But they are entirely different consonants for a Polish or Russian speaker.
L and R are just accents of the same letter in Japan, and different consonants in English.
And some people (like some French) have an accent because there are sounds they can not produce.